I'm leveling as frost. It looks like as soon as you learn frostbolt, you never really need to use frostfire bolt, or in other words, frostbolt replaces frostfire bolt.
I believe there's a proc called 'Brain Freeze' that grants you an instant cast of Frostfire bolt that you get at some level, and that's the only time you use it; until Legion that is, when they're changing its functionality