To catch the most rays, your back should be pointed straight at the sun. You want the smallest angle between the perpendicular to your back and the direction to the sun.
Bob will tan faster.
The diagram shows two more example vectors:
For ease in visualization the tails of the vectors have been placed at the origin. The vectors point into two different octants of 3D space.
Rotate the viewpoint to get a better idea of the two vectors. See if you can find a viewpoint that best shows the angle between the vectors.