We present a comprehensive investigation of the systematic and random errors of the nano-metrology instruments used to characterize synchrotron X-ray optics at Diamond Light Source. With experimental skill and careful analysis, we show that these instruments used in combination are capable of measuring state-of-the-art X-ray mirrors. Examples are provided of how Diamond metrology data have helped to achieve slope errors of <100 nrad for optical systems installed on synchrotron beamlines, including: iterative correction of substrates using ion beam figuring and optimal clamping of monochromator grating blanks in their holders. Simulations demonstrate how random noise from the Diamond-NOM's autocollimator adds into the overall measured value of the mirror's slope error, and thus predict how many averaged scans are required to accurately characterize different grades of mirror.