Exploration of optical properties of organic crystalline semiconductors thin films is challenging due to submicron grain sizes and the presence of numerous structural defects, disorder and grain boundaries. Here we report on the results of combined linear dichroism (LD)/ polarization-resolved photoluminescence (PL) scanning microscopy experiments that simultaneously probe the excitonic radiative recombination and the molecular ordering in solution-processed metal-free phthalocyanine crystalline thin films with macroscopic grain sizes. LD/PL images reveal the relative orientation of the singlet exciton transition dipoles at the grain boundaries and the presence of a localized electronic state that acts like a barrier for exciton diffusion across the grain boundary. We also show how this energy barrier can be entirely eliminated through the optimization of deposition parameters that results in films with large grain sizes and small-angle boundaries. These studies open an avenue for exploring the influence of long-range order on exciton diffusion and carrier transport.