Gauss' Law is primarily applicable when the electric field (E) is uniform and perpendicular to the surface (S) being integrated. In cases of complex geometries or non-constant fields, more in-depth integration is required. If E is not perpendicular, the integration involves the cosine of the angle between E and the surface normal. For non-uniform fields, one must integrate E with respect to the area element (dA) to accurately determine the flux. Overall, Gauss' Law is most effective in scenarios with high symmetry where E can be treated as constant.