64-bit Operating systems usually run 32-bit applications just fine.
you have add the /3gb switch to your boot.ini file if you put over 3gb in your 32-bit system.
In addition, whether or not you will benefit from 2gb of additional ram depends on your motherboard chipset, CPU, the type of ram you are currently running and the memory timings of the ram. It also often is affected by whether or not each ram stick is the same build and revision.
I bought two gig of DDR ram in a matched set to add to a system that already had 1gig of DDR ram in a matched set. While I'm able to run all 3gb in the system, the memory bandwidth is cut to less than half of what it is with just the 2gb installed.
So I'm running on the 2gb only until I have time to do more testing.
Bottom line, while everyone is talking about how much memory Photoshop needs to run optimally, Adobes site has some interesting info regarding that in the support section. You should go there and take a look.
Before buying any additional ram for your system do some research on your components and look specifically for information on what happens to the ram on your motherboard if you populate more than two slots, particularly if you are using dual data rate ram.