Improved materials, processing protocols, and device designs have brought organic electronic devices to the forefront of numerous emerging technologies. A key bottleneck, yet critical requirement, that remains is a thorough understanding of the relationships among molecular structure, processing protocols, solid-state packing, and the underlying physical processes that determine device performance. Here we will discuss the development of molecular-based models that provide relevant materials-scale information through the combination of classical molecular dynamics approaches with quantum mechanics calculations. Our goal is to provide a molecular-scale description of solid-state packing in order to assess the evolution of key electronic states in organic-based semiconducting active layers. These models represent an important step toward the development of integrated, multi-scale modeling approaches that will enhance our understanding of organic electronic materials.