How can I tell which files are safe to move?



If you don't know, don't move them. What exactly are you trying to do and why?

Generally, anything in My Documents, Music, Movies can be moved with no issues. Anything else, leave it alone. You can actually assign Windows to move the contents of My Documents to a different folder and drive automatically. Just right-click on My Documents, you will see a location option, change that to where you want it to live.