Disregarding relativity, yes, the angle between two vectors is invariant. An accelerating observer will see the same angle as a nonaccelerating observer. A rotating observer will see the same angle as a nonrotating observer. The angle between two vectors is as constant as things get.
When you throw Einsteinian relativity into the mix, the angle between two vectors is NOT invariant. Let's declare you to be at rest. You draw a square on the ground. Pick a corner. One side coming out of that corner is called "side A" and the other is "side B." Now draw a diagonal line from your corner to the opposite corner. Call this line "diagonal D." Now the angle between side A and diagonal D is 45 degrees, and so is the angle between B and D.
I get in my rocket and move at, um, 87% of the speed of light in a direction parallel to side B. Then when I look at the square, I'll see Lorentz contraction: side A will look the same to me as to you, but side B will appear only half as long. So from my perspective, the square is now a rectangle where the angle between A and D gets smushed to 27 degrees and the angle between B and D stretches to 63 degrees, but you still think it's a square and that the angles are 45 degrees each.
But again, if we ignore Einsteinian relativity, lengths and angles do not appear to change just because the observer is moving or accelerating.