Welcome to the forum!
I'm not sure how to interpret this
I'm a complete CAD and Inkscape beginner.
But just to possibly help you avoid confusion, Inkscape is not a CAD program. While they are capable of producing the same kind of drawing, they work in very different ways. Possibly you don't mean it that way, but just in case.
Another way to approach it, which is different from Moini's suggestion, is to use Snapping. Simply snap the circle's center to the square's center.
http://tavmjong.free.fr/INKSCAPE/MANUAL/html/Snapping.html Note that for snapping to centers or rotation centers, the objects must have a fill, to make the snap happen. But the fill can be removed afterwards, if it's not wanted.