Taskmaster isn't really trained, though. He has a superpower that allows him to mimic the skills of others. It's his power, not his training, that allows him to do what he does.
I also would not put characters like Spider-man in this category. While the quality of his training was excellent, he was only at it for several months. That doesn't compare with someone who has been trained for a large portion of his/her life. By the same logic I don't think Captain America fits. Cap is a brilliant natural fighter but he only had several years of training and experience before he was frozen alive.
There are several characters who have had very intense training, though for a fairly limited period of time (early adulthood to late twenties) like Moon Knight, Punisher, and Elektra all fall into this profile. While the results are impressive I wouldn't call them as well trained as someone who has been trained for a large portion of their life.
Iron Fist (Danny Rand) has been intensely trained in martial arts since the age of 8. I don't think it's been said how young Davos was, but his training must also have started when he was a child. Black Widow (Natasha Romanov) started her training as a young girl. Cat (Shen Kuei) once boasted that started his training at the age of three. Shang Chi countered that he began his training at the age of two.
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