What is the most painless way to kill an animal while hunting?
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There are two methods I know of: Bleeding the animal quietly with minimal trauma and disruption of the central nervous system.
Both methods fly in the face of conventional hunting culture which prefers high velocity rifles and maximum trauma and energy transfer to the body. The fact of the matter is all animals find supersonic booms and loud muzzle blasts in conjunction with being hit with decent amounts of unexpected force very scary. If they aren't paralyzed, they run.
Quiet bows with razor sharp broadheads that achieve pass through on the animal often go unnoticed. Silenced .22lr rifles using solid subsonic ammunition can achieve a similar effect with heart and lung shots, though the bullet will often fail to pass through on animals heavier than 80lbs, instead lodging just under the skin on the opposite side of the body. In either case the animal will be hit, look for any source of noise and go back to whatever it was doing without getting spooked. If it happens to see you it might run a few yards just to distance itself. Don't pursue it and scare it further, it will bleed to death soon enough.
Disruption of the central nervous system involves perforating the brain or severing the spinal cord of an animal. Bows are often unsuited for skull penetration because they fire a slower projectile with a longer time of flight and have a greater chance of deflecting off of round bony surfaces. All rifles on the other hand excel at skull penetration because they can be aimed with greater accuracy to hit flat surfaces at near perpendicular angles to prevent deflection. Most modern hunting weapons are unsuited for severing the spinal cord in a repeatable fashion, but outright decapitation of animals with bladed weapons is effective and relatively painless if you can get close enough. Breaking the necks smaller animals is common practice when processing them for meat.