Can electrons switch orbitals within a shell?
The short answer to this is: according to our current understanding of quantum mechanics, we can't tell.

And now for the long answer:

First off, if you haven't already seen Richard Feynman's 60-second primer to the scientific method, you should definitely watch it now. It's short. I promise I won't go anywhere while you're watching it.

...

Alright. So the way science works is to test ideas by experiment. This means that in order to distinguish between which of two ideas is right, we'll need to come up with some difference in their behavior. This can sometimes be problematic in science because the difference in behavior between two models can be incredibly small. To take just one example, it wasn't until the 20th century that an apparent error in the orbit of Mercury was confirmed, which was eventually explained by relativity. Before that, if you had given someone the theory of relativity and the Newtonian theory of gravity and asked them to tell you which one was right, they would have shrugged their shoulders. There simply wasn't enough high-quality evidence to decide between one or the other.

On the other hand, what if there's a nightmare situation in which we simply can't tell the difference no matter how good our instruments are? Imagine that I give you a small cube which lights up when you shake it, but I've used magic so that no matter what experiments you try to use to figure out what's inside of the cube, you can't get any information. You can try to use x-rays to image the inside, or weigh it, or spin it around to see if the insides are unevenly distributed, or look at it with an IR camera...but every single time, the magic renders your results useless.

Now suppose I asked you how the box worked. Without being able to get any info, you're stuck! No matter how clever you are in making your guess or how many guesses you come up with, you can't really say anything about any of them, because you're being magically prevented from getting information about what's in the box.

This is a very important idea, so I want to make sure you really understand it. Without some sort of actual behavioral difference that can be looked at, science has no way of distinguishing between alternate ideas.1

Now, quantum mechanics is sometimes a lot like our magic box (to pretty much anyone who tries to study it, it is a magic box). Our current understanding of QM says that we have this wavefunction that tells us what the system is doing. We can't actually look at the wavefunction. The best we can do is to use some operators on it, which will give us the values of certain properties (don't worry if this all sounds very mysterious, it takes years of study to understand some of this stuff).



So how can we see if the wavefunction matches what we think it is? Well, we can look at what we should get from the operators, and what we actually do get from measuring it. For instance, by applying something called the Hamiltonian operator to the wavefunction, we get the total energy of the system. We can then measure the total energy of the system and see if theory and experiment agree. We can do that a whole bunch of times, measuring the momentum, and kinetic energy, and the average position of the system. If we do it enough times, we can say "eh, it's probably correct" and then move on to the next problem.

Now, to get back to your original question: can electrons ever switch places? Well, our current understanding of quantum mechanics is that, when electrons switch places, the wavefunction changes sign.2 "Aha!" I hear you say. "So we can watch the wavefunction and see if it changes sign, and if we ever see it flip, we can say that the electrons switched places!"

Well...not really. Because we can't look at the wavefunction directly, we can only measure things through the operators. And here's where the nasty trick comes into play: for all operators that we can actually observe, there won't be any change if the wavefunction flips its sign.

We're stuck! Just like our magic box, we can't get any meaningful information about what's going on inside, and so we can't really tell if the electrons switched places. Even if they did, it would look exactly the same to us (no matter how good our instruments are, we cannot see a difference, because there literally isn't one). It's an undecidable problem!

Now, if you're anything like me, this is a really crummy and disappointing answer. It took me a long time to accept the fact that there are some things in science that we just can't decide. So let's get a little creative: what would have to change in science for us to be able to tell?

First, and most directly, we would need an alternate theory to QM that allows us to distinguish between the two cases. Seeing how incredibly complex current theories are, I doubt that will happen anytime soon (though I could be pleasantly surprised). The second is that we would need some way to measure the wavefunction directly, instead of looking at it through operators. I've heard whispers of groups making progress on that front, though I honestly don't know if there's any truth to that or not. One way or the other, I don't expect we'll be able to answer this question tomorrow, or anytime relatively soon.




Some time back, I heard about a very clever paper that had to deal with this problem. There was an effect that could either depend on the temperature or density of water. Of course, you can't control the temperature and density of water independently (the stuff expands when you heat it up), and so everyone had just assumed that temperature was responsible. This group realized that, if you supercool water, it takes on densities similar to those found above 0C. By carefully supercooling the water and measuring this effect, they found that at similar densities of water, the effect was the exact same, even when the temperature differed by over 50C. It was density that was responsible all along!
This is one of the most mysterious things about all of physics. Even after two years of studying quantum mechanics, I have yet to find anyone who can offer a satisfying explanation for why fermions (half-integer spin particles) should flip their wavefunction upon exchange of (ostensibly identical) particles. If you know of a good read on the subject, please put it in the comments and I'll add it here!