If you insert a smaller image into the 800 x 800 canvas, Paint 3D will center it by default
However, it will be centered as a rectangle - meaning, if you draw a circle around it, the CoA will not look centered
You need to think for the CoA to be rather a triangle, and then this would be centered if the 3 edges are at the same distance from the circle
So, as a rule of thumb, you need to lower the CoA a bit, for it to look centered
With some experience you can do this manually
But there are tools to calculate the exact position, and also templates for GIMP