Motivated by recent experimental studies of matter waves and optical beams in double-well potentials, we study the corresponding solutions of the nonlinear Schrödinger equation. Using a Galerkin-type approach, we obtain a detailed handle on the nonlinear solution branches of the problem, starting from the corresponding linear ones, and we predict the relevant bifurcations for both attractive and repulsive nonlinearities. The dynamics of the ensuing unstable solutions is also examined. The results illustrate the differences that arise between the steady states and the bifurcations emerging in symmetric and asymmetric double wells.