Plame hadn't been covert for years. She was brought home after the Aimes affair. She's an analyst trying to get into management. Wilson's probably hoping whatever Democrat he helps get elected will nominate her CIA director put of gratitude for all they've done for The Party.
Yes, her cover was blown by Ames. That means she was brought back and would not be sent overseas again. That means all the crap they were putting out there about endangering lives and operations overseas, blah, blah, blah, was ridiculous. That means the Act, which is all about intent, didn't apply to her.
But that doesn't mean she didn't have undercover status. While plenty of people knew she was agency, plenty of people, like her neighbors and friends, were under the impression she worked for another government agency because she was required to say that as a covert employee.
She wasn't an analyst at the time, more like an admin asst. to Alan Foley.