A Schubert variety in the complete flag manifold $GL_n/B$ is Levi-spherical if the action of a Borel subgroup in a Levi subgroup of a standard parabolic has a dense orbit. We give a combinatorial classification of these Schubert varieties. This establishes a conjecture of the latter two authors, and a new formulation in terms of standard Coxeter elements. Our proof uses the theory of key polynomials (type A Demazure module characters).