PAE won't help any in most user desktop situations, as it's usually gets limited by the hardware/bios and not the os. Both the hardware and the OS need to support pae for it to work.
In fact, most versions of windows run PAE mode automatically due to DEP by default being on, which requires PAE. Assuming windows xp sp2 or later. But then there still is a chance pae wont fully be enabled sometimes unless you define the switch... so its worth a try, but wont guarantee results.
Also, /pae is ok with xp too, not just vista.