You can't do an in-place upgrade from 32-bit to 64-bit, so the easiest way to migrate all your user data and settings is to use Windows Easy Transfer. I wrote a pretty big write-up on how to do it here: http://www.gamesas.com/topic/1337677-dtcs-still-a-veritable-nightmare-in-skyrim/page__view__findpost__p__20144729
Thanks for the info. I have everything backed up on my home server, so that "should" make things easier.
I'm still in research mode on picking my new hardware, so it will be awhile before I get around to it.