A comparative study of the electronic structure of methylammonium (CH3NH3) in organometallic lead triiodide perovskite (CH3NH3PbI3) thin films synthesized using either one- or two-step deposition protocols is performed using angle-resolved C K-edge soft X-ray absorption spectroscopy (XAS) and model calculations. We find that our XAS measurements can be accurately related to the ground-state unoccupied orbitals using a simple crystal field model. We further find that films made by the one-step deposition protocol exhibit angle-dependent features, indicating long-range alignment of the CH3NH3 molecules, although the angle-dependency decreases as the film thickness increases. No angle-dependency was observed in the films made via the two-step deposition method.