Each PSU has a 3.3 volt, a 5 volt and a 12 volt
Obviously, you dont want it too high or too low from those given values.
Testing it, or testing the output should be done under varying loads, such as a stressful game, where alot of your hardware is being used close to capacity, as well as at idle, and maybe a midpoint as well, maybe a less stressful game for instance.
If your voltage levels remain mostly stable, and dont dip or even possible peak high, then most likely your PSU is OK.
Then go from there, checking your cpus heat, see whats normal for it, as well as your gpus, as each component has its own operating temp/power draw