In this paper we analyze the novel quantum properties of atomic photo-excitations generated by Orbital Angular Momentum (OAM) photons. It was previously predicted for Bessel beams (BB), that transitionsin atomic systems driven by twisted laser beams obey a modified set of position-dependent angular-momentum selection rules. It was also shown, that in the case of perfect alignment of the atom on the beam axis, total angular momentum of the photon must be fully transferred to the internal degrees of freedom of the target, which causes dramatic enhancement of higher-multipole processes. As a result, weak atomic transitions, which are hardly observable in interactions with simple states of light, become accessible with OAM photons. In the current paper, we extend the earlier developed theory to describe atomic photoexcitations by Bessel-Gauss (BG) and Laguerre-Gauss (LG) modes. It allowed us to infer the information about the phase structure of the beam, such as mode content and topological charge. The formalism exhibits a high level of sensitivity to the polarization content of the laser beam, which is on the order of 0.005% of the polarization admixture. The theoretical predictions are confirmed experimentally for photo-excitation of Ca40+ ions, trapped in a micro-structured, segmented Paul trap. The full set of quadrupole transitions from the S-state were generated by 729nm OAM laser beam shaped with a holographic phase-plate with a fork-dislocation. The experiment was conducted by Ferdinand Schmidt-Kaler's group at the University of Mainz.