well, you never know for sure until you try yes, but here's a few possible reason.
1. your not going to mistake Paul Millsap as a center.
2. he's not 33 with bad feet
3. there's probably no political issue between him and Dwight.
I feel the biggest actual issue with Dwight and Pau was more political / health than actual game. i.e Dwight was unhappy to be in a situation where not only was he not the highest profile player, but may not even by the highest profile center . on top of that Pau was hurt for much of the year and even when he was on the floor just wasn't close to 100%.
At least my perception of Paul Millsap is that he would have little issue with being the 3rd option on a team. and that he can and often do score a lot in the flow (though he can score pretty well in an iso situation as well.).
I agree that Millsap's 3 point sample is not definitive enough to really say anything about him, but I'd feel if the Jazz are comfortable with him taking most of his limited 3s late in the game, it probably says a good deal of their confidence in his shooting as a whole.
(it should be noted that i don't actually agree that your 4 really should be just taking a million corner 3s and never gets in the paint.)