Just a thought... no clue if this would work, but worth a try... You can install most applications wherever you want as long as you do a custom install. What if you did the following:
XP32 (OS running on C: drive) - custom install steam to C:\games\steam.
XP64 (OS running on D: drive) - custom install steam to the same exact folder, C:\games\steam, if it recognizes it already exists, tell it to do something like a repair install. Worst case, it won't proceed, so rename the C:\games\steam folder to something else, say steam_old, then proceed with the custom install in XP64 to C:\games\steam
If this works, it shouldn't matter which OS you use to get steam to download the games, with luck, steam in the other OS will recognize all the same file binaries and profiles. If it does work, delete the steam_old dir as it's not needed anymore.