The whole structure is different in the 64-bit OS, and it uses WoW64 (Windows on Windows) such that 32-bit stuff will run.
Windows 32-bit versions could address more than 4gb, but the limit was set to preserve reliability and other issues that could crop up now and again.
In use, there is hardly any difference. W0W64 runs seamlessly with any application/program that is Windows 7 compatible. There are few exceptions to the rule, Lotus Smartsuite Millenium and Lotus Organiser are two that will only run properly in 32-bit, and also some small utilities which need to be bit-specific.
The only time where 64-bit hits a stop is hardware drivers which have to be 64-bit or else..