Instead of explaining it myself, I'll let someone who has to maintain a kernel with PAE support speak in his charming ways, Linus Torvalds
Also keep in mind that the PAE support in Windows 32bit versions comes for a lot of cash. XP won't even be able to make use of full 4 GiB of RAM normally, because MS chose to not enable PAE features on it. A kernel that is closely related, Windows 2003 Server, does support PAE. However, even there your "Standard edition" will only support up to 4 GiB (but working around the BIOS memory hole), whereas the more expensive editions will then allow up to 64 GiB of RAM. The same holds for 32-bit Vista.
However, not in all cases is this limitation imposed by Windows. If it were, booting a PAE-enabled Linux kernel would still enable you to use the full 4 GiB (or more). Not so, some hardware manufacturers chose to impose this limitation at the BIOS level, although the CPU and chipset would be capable of handling PAE.
Just a side-note: none of the current x86-based 64bit processors can even address the full range of the 64bit address space physically (for reference see this questionsee this question and answers).