Push Down Automatons "guess" - what does that mean?
Quite simply, the mechanism is magic. The idea of non-determinism is that it simply knows which way it should take in order to accept the word, and it goes that way. If there are multiple ways, it goes one of them.

Non-determinism can't be implemented as such in real hardware. We simulate it using techniques such as backtracking. But it's primarily a theoretical device, which can be used to simplify the presentation of certain concepts.

For the palindrome, you can think about it in two ways. Either there's a magical power that lets your machine say "this is the middle of the word, time to switch from pushing to popping", or after reading each letter, it says "I'm going to fork a new process which that this letter is the middle of the word, and see if it finds it's a palindrome. Then in this other thread, I'll keep trying, assuming this isn't the middle of the word".

Another way to think of it is as infinite parallelism. So an equivalent model would be that, instead of choosing a new path, it simultaneously tries both paths, branching off new "processes," succeeding if any are in a final state after reading the whole word. Again, this can't be built using real hardware, but can be modelled with non-determinism.

The interesting thing about nondeterminism is that for finite-automata and Turing machines, it doesn't increase their computational power at all, just their efficiency.