It actually depends on the machine as to how much it will see. 32 Bit XP/Vista has a maximum address space of 4gb, but other things count towards the addressable space (PCI devices etc) so that all reduces the total for RAM.
If you put the 4gb in, you will probably see about 3.3~3.7gb of it. Whether that is going to make a difference for you depends on your usage. I use 2gb in my Win7 laptop (was on vista) with no problem for general day to day stuff, but if you're doing something RAM intensive (photoshop etc) then you may benefit from a few 100 more mb.
I dont believe you can use the 64 bit with a 32 bit key as they are sold as different products - I may be wrong though.