So long as you collect it in a manner that's not going to introduce any contaminates into the water I don't see any issues. The only additive that should be used on a normal basis would be dechlorinator, and since rain water would be lacking chlorine (unless you live somewhere very strange) then no.
Ammonia shouldn't be an issue in a stable tank, and you shouldn't need to test for it unless something happens to impact the bacteria. If your tank isn't stable, then by all means test for it. As far as I know there isn't any accurate way to check ammonia levels without a test kit.