The line out is for sending a direct signal to a PA or mixing board, so that the engineer has another option besides miking your cabinet.
The extension speaker jack is for hooking up an external cabinet in addition to the speaker built in to the amp. Just make sure that if you do this, you select a cabinet that is 8 ohms. The built in speaker is an 8-ohm speaker, and connecting another 8-ohm cab would drop the total resistance to 4 ohms, which will then enable you to use the full 220 watts (right now with the built-in speaker you are only running at about 140 watts). If you hook up a 4-ohm cabinet in conjunction with the built-in cabinet, the resistance will be too low and too much power may flow through the amp and you run the risk of frying it. You might want to find a decent cheap 2x10 8-ohm cabinet to pair with the built-in 15.