The way I see it, the best form of execution would be something like a .50 caliber rifle shot to the head as it is 100% to be an instant death. The fact that something like lethal injections with higher rates of failure or very painful delays are used shows that people prefer a sanitized execution to a humane one.
I remember reading somewhere that the focus of modern execution methods isn't to be humane but to create psychological distance from the act of killing the person and honestly I 100% agree.