Photons carrying a well-defined orbital angular momentum have been proven to modify spectroscopic selection rules in atomic matter. Excitation profiles of electric quadrupole transitions have been measured with single trapped 40 Ca + ions for varying polarizations. We further develop the photo-absorption formalism to study the case of arbitrary alignment of the beam's optical axis with respect to the ion's quantization axis and mixed multipolarity. Thus, predictions for M1-dominated 40 Ar 13+ , E3-driven 171 Yb + and 172 Yb + , and B-like 20 Ne 5+ are presented. The latter case displays novel effects, coming from the presence of a strong photonmagnetic dipole coupling.