Direct detection of superconductivity has long been a key strength of point-contact Andreev reflection. However, its applicability to atomic-scale imaging is limited by the mechanical contact of the Andreev probe. To this end, we present a new method to probe Andreev reflection in a tunnel junction, leveraging tunneling spectroscopy and junction tunability to achieve quantitative detection of Andreev scattering. This method enables unambiguous assignment of superconducting origins of current-carrying excitations, as well as detection of higher order Andreev processes in atomic-scale junctions. We furthermore revealed distinct sensitivity of Andreev reflection to natural defects, such as step edges, even in classical superconductors. The methodology opens a new path to nano-and atomic-scale imaging of superconducting properties, including disordered superconductors and proximity to phase transitions.