If an unlicensed driver was driving your vehicle and got in an accident and totaled it will the insurance pay?

It depends on the conditions of your policy. If there is a clear stipulation that it will not cover any unlicensed drivers, or any drivers not specifically listed for that matter then no they won't pay. If such a condition is not specified and coverage is unconditional (in that respect) then they probably will.

Assuming the person survived, and was not taken to jail it is doubtful they would be civily liable for the damages to another victims car (if applicable) hence the policy owner who's name is on the title is ultimately liable.