For the calculation of core-excited states probed through X-ray absorption spectroscopy, the core-valence separation (CVS) scheme has become a vital tool. This approach allows us to target such states with high specificity, albeit introducing an error. We report the implementation of a post-processing step for CVS excitations obtained within the algebraic-diagrammatic construction scheme for the polarization propagator, which removes this error. Based on this, we provide a detailed analysis of the CVS scheme, identifying its accuracy to be dominated by an error balance between two neglected couplings, one between core and valence single excitations and the other between single and double core excitations. The selection of the basis set is shown to be vital for a proper description of both couplings, with tight polarizing functions being necessary for a good balance of errors. The CVS error is confirmed to be stable across multiple systems, with an element-specific spread for K-edge spectrum calculations of only about +/- 0.02 eV. A systematic lowering of the CVS error by 0.02 eV-0.03 eV is noted when considering excitations to extremely diffuse states, emulating ionization.