As Richard says, the 32-bit version should continue to work unless you've got a driver or a shell extension or something.
However if you do need to upgrade the code you're going to have to upgrade the compiler too: I don't think MFC got good 64-bit support until VS2005 or later. I'd suggest you get the 32-bit code building in VS2010 - this will not be trivial - and then start thinking about converting it to 64-bit. You can of course leave the production 32-bit builds in VC6 but then you add maintainership burden.
You'll probably get most of the way converting by flipping the compiler to 64-bit and turning on full warnings - particularly given the size of your code it may be impractical to review it all. One thing to watch out for is storing pointers in ints, dwords, etc. which may now be too short to hold the pointer - you need DWORD_PTR etc. now - but I think the warnings do catch that.
Or if this is in many components then you might get away with only migrating a few components to 64-bit. Then, unfortunately, you've got data length issues for communication between the two versions.