It's worth noting that retro-fitting unit tests into existing code is far more difficult than driving the creation of that code with tests in the first place. That's one of the big questions in dealing with legacy applications... how to unit test? This has been asked many times before (so you may be closed as a dupe question), and people usually end up here:
Moving existing code to Test Driven Development
I second the accepted answer's book recommendation, but beyond that there's more information linked in the answers there.
