GAE Users service can be used pretty much only for login to a specific GAE application, while Google+ sign in can be used to interact with any Google API. For example, if you need to know even a basic detail such as the user's full name, the Users service can't help you there.
The Users service is more "transparently coupled" to the user's session in Google - once the user has signed in, assuming they checked "remember me", they will keep being signed in as long as they don't delete the cookie, and you as a developer don't need to do any special check. With Google+ sign in you need to check whether the user is signed in on each visit and handle expired tokens yourself (though client libraries help with it).