The arrangement of semiconducting nanocrystals into ordered superstructures in which constituent particles can purposefully interact presents an attractive material platform to study fundamental light-matter interactions and develop programmable optical metamaterials. We investigated the processing-structure-property relationships of hierarchical assemblies of magic-sized CdS nanocrystals (NCs) to understand how chiroptical properties emerge from the geometrical arrangement of NC building blocks. Our bottom-up assembly involves the controlled evaporation of a colloidal suspension of monodisperse Cd37S18 NC between two parallel plates, which leads to the formation of hierarchical superstructures defined by the arrangement of 2 nm NCs into fibers, which in turn are arranged into uniform thin films with ~2 µm bands. The mesoscale anisotropic structure and associated optical properties of the NC fiber films share several similarities with liquid crystals. Remarkably, the films deposited on top and bottom surfaces exhibit opposite chirality. We describe symmetry breaking as a dynamic interplay between hydrodynamic and physicochemical processes during the formation of the hierarchical films. In-situ microscopy of the evolving band structure provides essential insights into the formation mechanism involving the shear-induced alignment of NC fibers and the subsequent mechanical relaxation of the stretched fibers to form band textures. We combine experiments and modeling to explain how processing conditions impact the wavenumber and amplitude of bands. We establish the foundational relationship between emergent chiroptical properties and the wavenumber of the undulation and attribute the strong optical anisotropies with g-factors as high as 0.06 to emergent mesostructure effects associated with the geometrical arrangement of the NC fibers within the film. The mechanistic insights from this study are consequential to enable future advances in the design and fabrication of programmable optical metamaterials for further development of polarization-based optics towards applications in sensing, hyperspectral imaging, and quantum information technology.