Proficiency and mastery come from deliberate practice. Work is often different.
I'm a programmer, which I consider a pretty high skilled job, and I'm losing my fucking time in my day job. Granted, I need to practice the craft to keep up. But there is a point where I should stop and just learn. I would learn much faster if I could just use 20% of my work time learning. And no, I can't do it on the weekends. This would be overwork, and I have a life.
Doctors are quite special: they deal with several cases a day. They encounter various situations, and their personal experience is by itself statistically significant. To them, more work will mean more data, and better trained instincts.
Programmers often work on less than 1 project a year. At that scale, personal experience is mere anecdotal evidence. More work will just mean some more anecdotal evidence. That's not nearly enough data to feed our instinct. Simply put, working full time is a suboptimal way to learn.
Now that I think of it, I bet even doctors would benefit from stepping back, and do some directed learning instead of just treating patients.