LTSpice capacitor network simulation question
The net N005 is a floating net, that means it does not have a connection to the rest of the circuit. Imagine that a charge was present on that net, it would be trapped and cannot leave!

In a simulator capacitors can be ideal meaning that the have an infinitely good isolation. For the circuit simulator it will then be a challenge to determine which capacitor is charged, C1, C4 or both have a charge? 

To prevent this the circuit simulator can (temporarily) add a very high value resistor (like 1000 Mohm) to the circuit to help it find a solution. That can explain why you see the 2 mV, net N005 is pulled down by this resistor which the simulator added.

On your bench things are very different. Capacitors are not ideal and have leakage. Obviously the 100 uF capacitor leaks a lot more than the 10 uF one and that pulls the voltage at N005 up and you measure 26.5 V.

If you measure with a normal voltmeter, realize that it has a 10 Mohm input impedance, that can cause a current to flow in the same order of magnitude as the leakage currents of the capacitors. That means your meter influences the voltages you're trying to measure.