NOTE: This will only resolve to someone who has actually assumed office. If anyone currently listed isn't confirmed by the senate, their name will be replaced with whoever the next person nominated is until someone's in the office on a permanent basis. (In the event Trump lets a temporary appointment stay in that role with no intention of replacing them, I'll just add them after a few months).
These are the 24 members of Trump's cabinet (his 16 "proper" Cabinet members + his 8 Cabinet-level members). Which role will be vacated first? Quitting, being fired, resigning in disgrace, dying - the method by which they leave doesn't actually matter for the purposes of this question.
In the unlikely event Trump makes it all the way through his term with none of these people leaving his cabinet, this question will resolve N/A.
In the unlikely event Trump dies, this question resolves to Vance (since he will have become the president, which is not a cabinet position).