We combine scanning-tunneling-spectroscopy experiments probing magnetic impurities on a superconducting surface with a theoretical analysis of the tunneling processes between (superconducting) tip and substrate. We show that the current is carried by single-electron tunneling at large tip-substrate distances and Andreev reflections at smaller distances. The single-electron current requires relaxation processes between the impurity-induced Shiba bound state and the quasiparticle continuum, allowing us to extract information on such relaxation processes from our analysis.