The leading electronic mechanisms of relativistic effects in the NMR magnetic shieldings of heavy-atom (HA) containing molecules are well described by the linear response with elimination of small components model (LRESC). We show here first results from a new version of the LRESC model written in terms of localized molecular orbitals (LMOs) which is coined as LRESC-Loc. Those LMOs resemble "chemist's orbitals", representing lone-pairs, atomic cores, and bonds. The whole set of relativistic effects are expressed in terms of non-ligand-dependent and ligand-dependent contributions. We show the electronic origin of trends and behavior of different mechanisms in molecular systems which contain heavy elements that belong to any of the IB to VIIA groups of the periodic table. The SO mechanism has a well-defined dependence with the LPs (LPσ and LPπ) when the HAs have them, but the non-SO mechanisms mostly depend on other LMOs. In addition we propose here that the SO mechanism can be used to characterize interactions involving LPs and the non-SO mechanisms to characterize covalent and close-shell interactions. All our main results are in accord with previous findings, though we are now able to analyze them in a different manner.