The chainwheel should be set to the Rohloff chainline, which is the distance from the centreline of the bike to the centre of the sprocket teeth. There are several different Rohloff chainlines depend on sprocket type and number of teeth; check the manual for your particular sprocket. If you can't find a chainline number for your Rohloff, work with 54mm, the most common. The tolerance is 1mm, which is real tight for amateur assemblers because the measurements are difficult to take consistently.
Okay, now forget the theory of the "centreline of the bike" because in practice it is impossible to work from there. Instead put a piece of masking tape all the way around the seat tube but not overlapping at the ends, to protect the paintwork. Now use vernier calipers to measure the thickness of the seat tube where the masking tape is fitted, including the two layers of the masking tape, and the thickness of your chainring. Add the two measures together and divide by two. Call this Result A. Now measure from the outside of the chainring to the far side of the seat tube; this is Result B which consists of a layer of masking tape, a seat tube, some air, and the width of the chainring. From B subtract A and this is Result C, which is the chainline.
If you don't have vernier calipers, a less accurate measurement than with vernier calipers can be taken with a simple ruler. Look up the seat tube diameter in your bike specifications. With the ruler up against the seat tube at its nearest approach to the chainring, measure to the centre of the chainring. Add half the seat tube diameter. The sum is the chainline.
Good luck.