From my own experience with it, I wouldn't recommend git as an introduction to version control. I've been using it for a couple of months now, and my impression is that it's very powerful and - now that I've partially got my head around it - reasonably intuitive. However, the learning curve is very steep, even though I've been using version control for years. It also suffers from being too expressive - it supports many different workflows and development models, but the only guidance on "the best" way to use it is a few pages deep in a Google search, which also makes it tricky for a newcomer to pick up.
That said, it's possible that starting from a blank slate with git might actually be easier - my VCS experience is all with centralised version control (CVS, SVN, Perforce...) and part of my (ongoing!) difficulty with git has been understanding the implications of the distributed model. I did glance briefly at other DVCSes like Bazaar and Mercurial and they seemed to be somewhat more newbie-friendly.
Anyway, as others have said, Subversion is probably the easiest way to get used to the version control mindset and get practical experience of the benefits of VCS (rollback, branches, collaborative development, easier code review, etc).
Oh, and don't start with CVS. It's still in practical use, and has advantages, but IMHO it has too many historical quirks and implementation problems (non-atomic commits!) to be a good way to learn.