Plastic materials are ubiquitous and raise concerns about their impact on health and the environment. To address these concerns, it is crucial to characterize the structural, size, and textural properties of plastics throughout their lifecycle from production to degradation. Raman spectroscopy appears as a valuable tool for this purpose, offering speed, robustness, and sensitivity to nanoscale and amorphous particles. In order to be properly used for plastics, the Raman response of reference materials needs to be carefully assessed, with the literature on such assessments being scarce. This study addresses this gap by using theoretical calculations to generate ab initio spectra for polystyrene, a reference material. The aim is to explain the origins of the spectral peaks and their consistency across various compositions and structures using linear ordered polymeric and finite amorphous models. The CRYSTAL package is employed to obtain full Raman spectra based on a careful benchmark of computational settings. While some peaks are present across all spectra and can serve for calibration, others exhibit structure-dependent behavior, enabling polymer identification. We conclude that Raman spectroscopy is a well-suited technique for plastics characterization provided that a careful analysis of signal origin is conducted to fully interpret the spectra and deploy applications.