You could then get Robin Williams from Mrs. Doubtfire or Dustin Hoffman from Tootsie as nominees.

Robin Williams played Daniel Hilliard. It was the character Daniel Hilliard who played Mrs. Doubtfire.

Dustin Hoffman played Michael Dorsey who played Tootsie* (Dorothy Michaels)

Not even Stephen Rea in The Crying Game was playing a female character.

*I'm not even sure that the name Tootsie referred to the Dorothy Michaels impersonation.