Coupled quantum wells have been proposed as candidates for highly polarizable structures due to their near-degenerate and dipole-coupled electronic states. Hence, many interesting applications in linear and nonlinear optics can be envisioned. We analyze this proposal considering a simple structure with a delta-function barrier separating the wells. While very substantial Stark shifts are certainly predicted for this geometry, perturbative estimates based on polarizabilities (and hyperpolarizabilities) fail beyond a critical field strength that depends inversely on the barrier. Hence, a giant Stark effect due to near-degenerate states is invariably limited by a small critical field. Our analytical (hyper) polarizability expressions are applied to find quantitative Stark shifts for GaAs quantum wells and transition-metal dichalcogenide bilayers. The predicted Stark shifts and critical fields agree with the field dependence observed in a range of available experiments.