Particle accelerators are a leading tool for frontier science. Pushing that frontier further demands more machines with higher performance, and more of a very expensive technology: superconducting radio-frequency (SRF) acceleration. From a materials perspective this means reducing residual surface resistance or raising the operating temperature (currently ~2 K) of SRF cavities. Both are pursued by materials modification: nitrogen doping/infusion in the first instance and coating with Nb3Sn in the second. Materials characterization is key to achieving understanding and directing RandD. However, very little has been done. This present work aims to fill the knowledge gap and to provide needed, validated tools to the accelerator science community. In this connection, SIMS, XPS and EBSD have proven especially valuable and represent the majority of discussion in this dissertation.