Hey Dan,
While it is "safe" it isn't a "just flip" process, I'm afraid. There is the virtual->virtusers table conversion that has to happen, and I don't believe there is any automatic way to accomplish that. I just replied to a query about the opposite conversion here:
http://www.virtualmin.com/forums/message-view?message%5fid=50612Once I have examples of both types of file, I'll be making a little perl script to do either conversion automatically.
The aliases files are probably fine, though you'll probably want to clean up the extra usernames (the ones without @ in them). There are probably one or two other things to keep in mind, though I'm so unfamiliar with Sendmail that it's hard for me to predict exactly what.