So the power_good green wire then. Yah that should work on boards with dual AT/ATX connector, but might have weird or even bad effects on a pure ATX board. Should use an ATX supply with it's own switch on the back, because slots may still have standby power when PG switch off, so you need to switch PSU off or unplug to change or install a card.
However, just using this one switch, you might have problems if software puts system into suspend or sleep power states, where normally a tap on the ATX power button would wake it up. On some boards the BIOS lets you set keyboard power on, so tapping spacebar would wake it up. This may also be necessary on boards that are more ATX than AT to get them to start.
Alternatively, there are some types of power switch of the push and latch variety, that have their latch springs on the outside of the switch, so you can pull them out and it becomes a momentary switch with no latch. So that type you could mod to no-latch and hook up to the power switch pins.
Some problem that occurs after a period of time with higher AC or high DC rated switches used at low volts, low amps is that the contacts oxidise, where at higher voltages and currents they would self clean from the slight arcing. This varies by switch design.
Unicorn herding operations are proceeding, but all the totes of hens teeth and barrels of rocking horse poop give them plenty of hiding spots.