Hmmm something I may be able to help with. Our PSUs typically have an AUX and MAIN voltage output for 12V that is controlled by a smart voltage controller. Basically it will sequence some to most of the voltage rails in your system to turn on at certain times during bootup. This all happens within a second, but there are quite a lot of things that need to be checked and powered on during this ~1sec.
I can't share where to best strap this PS_ON_N, but I can give some general advice. The PS_ON_N is an input into the PSU to turn on the MAIN 12V rails. If these rails are on at the start, the GPU and other devices that require the BIOS to be awake first may not act correctly or in an unexpected behavior due to the design of the sequence I mentioned. If you have a DMM or an oscilloscope, you can probe around the 8pin power connector to figure out which is the PS_ON_N signal by simply applying the power button and waiting for one of those signals to transition from a high voltage (3.3V or 5V) to 0V. If you find that transition, that will most likely be the PS_ON_N signal. If you don't have those tools at hand than you'll be a bit out of luck.