PRG is perfect for browser Back button support too. An HTTP redirect replaces the URL in browser history instead of adding a new entry. If you apply PRG consistently, i.e. you always return a redirect from a POST, then browser history will only contain "safe" pages (GET), there will never be a POST URL in the history.
There is still a chance of getting duplicate form submissions, though. For example if the user double-clicks the submit button. So if you want to be extra safe you need some extra mechanism (e.g. nonce) to prevent double submissions.