This paper deals with the “modern” plaster mortars based on air lime, hydraulic lime, and cement used between the 1950s and 1990s of the last century, taking, as a case study, a historical building of the Cagliari city whose foundations and ground floor are cut into in-situ limestone. Different plaster layers (i.e., arriccio and intonachino, paint), applied on the excavated limestone walls, were collected from cave-room. All samples were analysed by optical and electron (SEM-EDS) microscopy and X-ray diffractometry (XRD) in order to define their microstructures, textures and compositional features. In addition, real and bulk density, water and helium open porosity, water absorption kinetic, and saturation index were measured. By microscopic imaging analyses, the binder/aggregate ratio as vol.% was determined. Results revealed that cement mortars, composed mainly of C-S-H, C-A-H, and C-F-H phases, given their high hydraulicity, low open porosity, and a rigid behaviour, showed a good chemical but not physical–mechanical adherence, as they were often found detached from the substrate and frequently loaded with salt efflorescence. On the contrary, the hydraulic lime-based mortars, characterised by a binder composed of C-S-H and C-A-H phases and calcite derived from the portlandite carbonation, showed a greater affinity with limestone substrate and other plasters. Thus, they are more suitable to be used as a repair mortar, showing a long durability on the time. The thin air lime-based plasters (intonachino) showed a good adhesion to the substrate, exerting their coating function better than the harder, cement-based mortars. Lime-based wall paints have a good chemical adhesion and adaptability to the irregular surface of the substrate, due to low thickness of lime paint layers (<1 mm) that confers an elastic physical behaviour.