Vice President: A Succubus--Any succubus--summoned from the Beyond and ensnared for the length of the administration by American ingenuity. Besides giving the whole Biden regime a probable sex-positive position, the resulting shenanigans of the Secret Service having to protect BOTH Joe Biden from the succubus and the succubus from the touchings of Joe Biden would make a wonderful pay-per-view, drama-infused reality-show that could be sold and used to pay-down the national debt (and/or the Treasury Secretaries ideas). I'm envisioning chase scenes through the White House halls set to Yakkety-Sax as the succubus tries to get at that man-meat, Biden tries to sniff the gorgeous hair, and the Secret Sevice agents desperately try to stop either from happening!
State: Alexandria Ocasio-Cortez, for the amusing policy-based catfights which would ensue between her and Biden's neoliberal orientation.
Treasury: Andrew Yang, to fully fulfill that 'money printer go brrrrrr' joke.
Defense: Tulsi Gabbard. For maximum 'Team of rivals' Cabinet fireworks.
Attorney General: James Mattis. Because I don't know how the attorney general works but don't see how the man is supposed to have authority as a General when he's just some law-nerd. Plus the clashing ideas between him and Gabbard in his old spot would be PRIME entertainment.
(incidentally, the Surgeon General should also be James Mattis)
Interior: Theodore John Kaczynski. Might as well piss everyone off.
Agriculture: Mike Rowe. It's a dirty/dull job, but somebody's gotta do it.
Commerce: Bernie Sanders. Might as well piss everyone off.
Labor: Jeremy Corbyn. Because the man has experience already heading Labour--and the colonial institutions lack of unnecessary 'u' might piss the Brits off in a subtle way.
Transportation: Elon Musk.
Energy: Monty Burns. Or his voice-actor, if cartoon characters are for some reason ineligible for the position.
Education: Keep Betsy DeVos. For the fireworks and WWE-style catfights which would develop (she can maybe organize them into an official, WH-sanctioned event!).
...Oh no! I confused DeVos with McMahon! That's embarassing (but, then, I never watch wrestling so...maybe excusable). So DeVos can just be an advisor to McMahon. SOMEONE in the Cabinet needs experience organizing dramatic fights, dangit (besides Mattis--those fights are too one-sided and no fun to watch)!