I believe the superior Acronis free versions can image over your choice of partitions. You can change drive sizes during cloning, however I don't recall if you can select partitions.
You can check the alignment after imaging using this: SSD Alignment
What I would do is try the imaging using Acronis or your favorite program, then check alignment and see how performance pans out. We have had good reports only so far that I have seen even though it was originally thought to be inadvisable.
If you're not seeing faster instananeous performance then I would re-install windows 7
following the tips in this link (which apply) to get a purrfect install you'll never have to reinstall again thanks to backup imaging.
You can ask in our Office forum about ways to automate moving the accounts/passwords.