Site-selective spectroscopy is a tool that can be used to uncover the presence of multiple sites available to optically active ions in host lattices. In this Article, we present techniques that can be applied to appraise the different sites that may occur in systems where charge compensation is required or in systems where such compensation is not present. We then consider some garnet crystals doped with chromium ions. For the Cr-doped garnets (YAG, GGG, GSGG, and CYMGG), we present luminescence and lifetime data over a wide temperature range, and infer not only the presence of different centers, but also the interaction among them as a function of temperature.