There are two problems you need to solve here.
The first is how browsers typically handle the back button. You should use a POST request to get to the page that the back button should not have access to. Most browsers will use a local cache for GET requests,, so if you do a GET, your server simply won't be accessed at all. A POST request will however typically perform a new request. Many browsers will also warn the user, and show a dialog box saying i.e. "Are you sure you want to send the form again?". So by using a POST, you increase the likelihood that every page load of that page will perform a new request to your server.
You may also be able to use a GET request where your server returns HTTP headers that makes browsers not load the page from the cache. Experiment with this.
The second problem is to make sure you invalidate duplicate requests server side. The first solution I can think of is to generate a token that you submit with the form and store in a database on every request. If a request is performed with a token that already is stored, you can invalidate the request. Perhaps there are better techniques, but I'll leave that as an exercise for the reader ;)