Billey-Postnikov (BP) decompositions govern when Schubert varieties $X(w)$ decompose as bundles of smaller Schubert varieties. We further develop the theory of BP decompositions and show that, in finite type, they can be recognized by pattern conditions and are indexed by the order ideals of a poset $\mathsf{bp}(w)$ that we introduce; we conjecture that this holds in any Coxeter group. We then apply BP decompositions to show that, when $X(w)$ is rationally smooth and $W$ simply laced, the Schubert structure constants $c_{uv}^w$ satisfy a triangularity property, yielding a canonical involution on the Schubert cells of $X(w)$ respecting Poincaré duality. We also classify the rationally smooth Bruhat intervals in finite type (other than $E$) which admit generalized Lehmer codes, answering questions and conjectures of Billey-Fan-Losonczy, Bolognini-Sentinelli, and Bishop-Milićević-Thomas. Finally, we show that rationally smooth Schubert varieties in infinite type need not have Grassmannian BP decompositions, disproving conjectures of Richmond-Slofstra and Oh-Richmond.