There's a few good tools out there that analyze disk space usage, like Disk Inventory X. They'll give you a better breakdown compared to what "About this Mac" offers.
One thought: I seem to remember that files in the Trash are counted under "System".
Taking it from another angle: There's not many file types that will fill up 750GB. Movie collections or massive photo libraries are the first that come to mind. If those are in an unusual location, the system may be counting them in the wrong category. Are you sure those are accounted for?