We address the intrinsic polarization and screening of an external electric field in a broad range of ordered and twisted configurations of multilayer graphene, using an ab initio approach combining density functional theory and the Wannier function formalism. We show that multilayer graphene is intrinsically polarized due to the crystal field effect, an effect that is often neglected in tight-binding models of twisted bilayer graphene and similar systems. This intrinsic polarization of the order of up to a few tens of millielectronvolts has different out-of-plane alignments in ordered and twisted graphene multilayers, while the in-plane potential modulation is found to be much stronger in twisted systems. We further investigate the dielectric permittivity epsilon in same multilayer graphene configurations at different electric field strengths. Our findings establish a deep insight into intrinsic and extrinsic polarization in graphene multilayers and provide parameters necessary for building accurate models of these systems.