Atomic multipole moments are used to investigate vibrational frequency shifts of CO and H-2 in uniform and inhomogeneous electric fields using ab initio calculations and Molecular Dynamics (MD) simulations. The importance of using atomic multipole moments that can accurately represent both molecular electrostatics and the vibrational response of the molecule to changes in the local electric field is highlighted. The vibrational response of CO to applied uniform and inhomogeneous electric fields is examined using Density Functional Theory calculations for a range of test fields, and the results are used to assess the performance of different atomic multipole models. In uniform fields, the calculated Stark tuning rates of Delta mu 0.52 cm(-1)/(MV/cm) (DFT), Delta mu = 0.55 cm(-1)/(MV/cm) (fluctuating three-point charge model), and Delta mu 0.64 cm(-1)/(MV/CM) (Multipole model up to octupole), compare favorably with the experimentally measured value of 0.67 cm(-1)/(MV/cm). For H-2, which has no permanent dipole moment, CCSD(T) calculations demonstrate the importance of bond-weakening effects in force fields in response to the applied inhomogeneous electric field. Finally, CO in hexagonal ice is considered as a test system to highlight the performance of selected multipolar models in MD simulations. The approach discussed here can be applied to calibrate a range of multipolar charge models for diatomic probes, with applications to interpret Stark spectroscopy measurements in protein active sites.