The best way would be to do a
header("location: form.php"); call after you process the form. That would redirect you back to the form page, and if you refresh, the browser wont resend the form data.
Alternatively, you could check to see if you already processed the data received, but that would still give you the browser warning message that you are going to resend the data.
You might do both, just in case someone uses the back button and accidentally clicks Submit again.