When John Hamm wears makeup - no, it isn’t appropriation because he’s wearing masculine makeup and you can’t even tell he’s wearing any. If he was wearing noticeable makeup (like pink lipstick and black eyeliners, etc) then that would be appropriation.
When Marc Jacobs wears a skirt - Yes! That is appropriation! I’ve seen photos of him in a pink dress before, it looks like he’s making fun of the female gender. However, he also wears kilts - kilts are not ‘skirts’, they’re not appropriation (unless you’re not Scottish, obviously).