Stimulated Brillouin scattering (SBS) is traditionally viewed as a process whose strength is dictated by intrinsic material nonlinearities with little dependence on waveguide geometry. We show that this paradigm breaks down at the nanoscale, as tremendous radiation pressures produce new forms of SBS nonlinearities. A coherent combination of radiation pressure and electrostrictive forces is seen to enhance both forward and backward SBS processes by orders of magnitude, creating new geometric degrees of freedom through which photon-phonon coupling becomes highly tailorable. At nanoscales, the backward-SBS gain is seen to be times greater than in conventional silica fibers with 100 times greater values than predicted by conventional SBS treatments. Furthermore, radically enhanced forward-SBS processes are times larger than any known waveguide system. In addition, when nanoscale silicon waveguides are cooled to low temperatures, a further times increase in SBS gain is seen as phonon losses are reduced. As a result, a segment of the waveguide has equivalent nonlinearity to a kilometer of fiber. Couplings of this magnitude would enable efficient chip-scale stimulated Brillouin scattering in silicon waveguides for the first time. More generally, we develop a new full-vectorial theoretical formulation of stimulated Brillouin scattering that accurately incorporates the effects of boundary-induced nonlinearities and radiation pressure, both of which are seen to have tremendous impact on photon-phonon coupling at subwavelength scales. This formalism, which treats both intermode and intramode coupling within periodic and translationally invariant waveguide systems, reveals a rich landscape of new stimulated Brillouin processes when applied to nanoscale systems.