Electron spectroscopy provides access to fundamental properties of solids, such as the geometric, electronic, and the magnetic structure. The latter are necessary for the understanding of a variety of basic but nevertheless important effects. The present work outlines recently developed theoretical approaches to electron spectroscopies. Most of the collected results rely on first-principles calculations, as formulated in multiple-scattering theory, and are contrasted with experimental findings. One topic involves spin- and angle-resolved photoelectron spectroscopy which is addressed for magnetic surfaces and ultrathin films. Exemplary results comprise magnetic dichroism in both valence-band and core-level photoemission as well as the temperature dependence of magnetic properties of ultrathin films. Another topic is spin-dependent ballistic transport through planar tunnel junctions, focusing here on the zero-bias anomaly. In most of the cases, spin-orbit coupling (SOC) is an essential ingredient and, hence, favors a relativistic description. Prominent effects of SOC are illustrated by means of the electronic structure of rare gases adsorbed on a substrate and by the splitting of surface states on Au(111). Concerning magnetism, the magnetic anisotropy of Ni films on Cu(001) is discussed, focusing in particular on the spin reorientation transition induced by lattice distortions in ultrathin films.