Hi Nick, welcome to PCHF.
What ever you do, don't touch that red switch at the back of the
PSU, it will pop, and you'll end up with a dead power supply! If you have done this already, then this will be the reason why your PC is not starting up.
The + and the - onboard the motherboard for the power button, doesn't matter which way around that goes, since all you have between them is a microswitch. With a microswitch, all it does is make contact between the two wires so it doesn't matter which may it is plugged in. What we tech's sometimes like to do (if we think that the microswitch/power button may be faulty or broken, is to make contact between those two pins with a screw driver, but you need to be absolutely sure of the two pins your touching before you do it.
And finally, make sure that you have enough power (wattage) in your power supply by using:
eXtreme Power Supply Calculator Lite v2.5 (click goLite).