Hi,
The centroiding precision should be proportional to the flux signal-to-noise divided by the PSF width -- narrower PSFs or brighter stars can be centroided more accurately, assuming no saturation.
There will also be some error due to our matching. In theory, matching four stars should reduce the error, but only on the position of the center of the matched quadrangle. Any rotation or scale errors in the matching will result in a WCS solution that is good in the middle of the matched set of stars but drifts away with distance from the center. Our "tweak" algorithm tries to find additional stars that match and uses those to nail down the solution, but this doesn't always work...
In short, "it's hard to say". :)
--dstn