Yes, you can always swap the washers around.
Much of it also depends on the distance between the brake bosses and the width of the rim itself.
These are 2.35s (actually they were 63mm wide, which is nearly 2.5") with Tektro Vees. Plenty of space left at the front, but at the back I had to swap the washers around because the brake's arm was too close to my liking.
I reckon you can easily put a 3" tyre in any set of Vees, especially so if you use the correct rims for your tyre's width.
(Schwalbe recommends at least 21mm inside the rim for the 2.35 Big Apple, I was running them on 17mm rims and to stop the sides from tearing I lowered the pressure to 3.5bar at their suggestion)
Closeup front
Closeup rear
Of course there might be issues if you want to remove the wheel if the tyre is still inflated.
On my old Dale the pads would hit the fork when I loosened the brakes and still not have enough clearance for the tyre to slide through. Same story at the back.