Progression within ANG is generally seniority based.
Someone joining as a FO either on the Classic Dash, Q400 or F100 should expect his/her next position to be a Classic Dash Captain (although Q400 command is possible if demand is there) then either Q400 or F100 Captain.
The move to the 737 and 767 requires command time on the F100 and then it would be initially to a FO position.
Not too sure how quickly you want to get "valuable jet time" but the trek to the 737/767 is not an "overnight" task.
Take this as very much a generalisation as to what presently happens there, but it should give you an idea of how they work the progression.