X-ray metal L-edge spectroscopy has proven to be a powerful technique for investigating the electronic structure of transition-metal centers in coordination compounds and extended solid systems. We have recently proposed the Restricted Open-Shell Configuration Interaction Singles (ROCIS) method and its density functional theory variant (DFT/ROCIS) as methods of general applicability for interpreting such spectra. In this work, we apply the ROCIS and DFT/ROCIS methods for the investigation of cluster systems in order to interpret the Ca and Ti L-edge spectra of CaF2 and TiO2 (rutile and anatase), respectively. Cluster models with up to 23 metallic centers are considered together with the hydrogen saturation and embedding techniques to represent the extended ionic and covalent bulk environments of CaF2 and TiO2. The experimentally probed metal coordination environment is discussed in detail. The influence of local as well as nonlocal effects on the intensity mechanism is investigated. In addition, the physical origin of the observed spectral features is qualitatively and quantitatively discussed through decomposition of the dominant relativistic states in terms of leading individual 2p-3d excitations. This contribution serves as an important reference for future applications of ROCIS and DFT/ROCIS methods in the field of metal L-edge spectroscopy in solid-state chemistry.