Spock
One character who sports multiple colours is Spock. He usually appears in science blue:
But here he is with command gold in the first episode of TOS, "Where No Man Has Gone Before":
Out-of-universe, they hadn't settled on his uniform yet. But in-universe, it's completely compatible with the fact that he is both First Officer and Chief Science Officer, and so he is in two divisions at once.
And now here he is in red in The Wrath of Khan:
Of course, all Starfleet officers of that era wear red jackets, but Spock's uniform here is adorned with command-level brass, as he is the Captain of the Enterprise in this particular screenshot.
In a sense, command-level is white in the film era, designated by the white turtleneck beneath the jacket and the white shoulder strap.
In contrast, medical officers like McCoy have a dull green turtleneck and strap. Saavik is a lieutenant junior grade, and her red turtleneck and strap coincide with this. Engineers have gold turtlenecks and straps.
So one can say that Spock is seen with three colours: gold, blue, and white.
Now, that's three colours but only two divisions, since gold from TOS and white from the film era have the same meaning.
However, since the original question question cites Sito Jaxa's red Academy jumpsuit as a divisional colour (indeed, Starfleet Academy is considered to be the fourth division), here is Spock with his charcoal instructor's uniform from the 2009 film:
So that makes for blue (science), gold / white (command), and charcoal (Academy instructor).
Wesley Crusher
Counting the Academy as a Starfleet division makes Wesley Crusher another candidate, as @ThePopMachine points out. Wesley wears command red, operations gold, and his red-topped Academy jumpsuit, all in TNG:
We also see Wesley in his grey acting ensign uniform, although it is unclear which "division" it designates (if any).
