I have been building an app for facebook now for a couple months. It works great, however, I can’t offer you any advice as you don’t sound like you know much php. Maybe you should try drupal.
As far as I know, CI can only do about as much as you see in the 20 minute blog tutorial. FB app is pretty much out of the question. I think you need to use Rails for something like that. FB is coded in PHP, so a PHP-based app would just clash.
Actually, if it is a payment app I recommend building it in Javascript. That way you can validate all the data before it is sent to the server. That will save processing time once the data gets there as you won’t have to check it.