Can I say that a competitive inhibitor (CI) binds to an enzyme's active site
about as equally well as the substrate, that's why when the substrate
concentration overwhelms the CI concentration, the probability of CI binding to
the enzyme can be ignored?
No. A competitive inhibitor will have its own intrinsic affinity for the
substrate binding site, which may be better (tighter) or worse than that of the
substrate. Even much better or much worse.