3d^2 vanadate perovskites exhibit an unusual phase diagram where the low temperature orbital and spin orders are strongly dependent upon the rare-earth cation size. Here, we demonstrate the delicate role of strain in epitaxial LaVO3 films by performing low-energy muon spin spectroscopy and ellipsometry measurements. The electronic structure is revealed by the measurement of the multipeak structure of the charge excitations. The analysis highlights the independent roles of the d_xy band confinement and the d_zx, d_zy doublet polarization for the orbital ordering to establish.