cycles per second
Join Date: Oct 2003
Bikes: Vitus Aluminum, DiamondBack Apex, Softride Powerwing 700, "Generic" Ishiwata 022, Trek OCLV 110
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Wheel off center and brakes off center are really separate issues
Wheel off center: To check if it is the wheel or the forks, flip the wheel around. If it is still off center to the same side, it is the forks. If it is off center but the other side, it is the wheel. An off-center wheel can be centered by adjusting the spokes.
You are correct that the centering screw is meant for minor adjustments. If the brakes are drastically off center, the method you describe is the correct procedure *but* first put the centering screw in less extreme position so that it can be later used for fine adjustments. If it is all the way out or all the way in, you may not be able to adjust adequately.