No, typically your Collision coverage (or a third party Property Damage Liability claim) would not pay to have your whole car painted after being repaired due to a covered loss. Normally if your car needs any area painted, that was damaged and repaired, they pay to have that portion of the car color matched and the paint blended so that the newly painted area does not stand out from the rest of the car. They do not however pay to have the whole car re-painted if only one area was damaged.
For instance if one door was dented do to an accident than the insurance would pay for the repair and paint for that door. If the door's paint job did not blend in well with the rest of the vehicle usually you request that they redo it and fix the issue, not paint the whole car.
If there is extensive damage to the vehicle where many parts are replaced or repaired and need to be painted there may be a need for the whole car to be painted however this would be rare since if there is that much damage an insurance company would usually total out the vehicle and thus pay the actual cash value to the owner and not try to repair it.
If you want your whole car painted after work is done and the insurance company is only willingly to pay for the affected area(s) than normally you can pay the difference yourself out of pocket to the body shop and get the whole car painted.
If you have a claim in with your insurance company that involves painting your vehicle speak to the claims adjuster working your claim to see what he or she says about the percentage of the vehicle they will pay to paint as part of your claim.