We numerically isolate the limits of validity of the Landauer approximation to describe charge transport along molecular junctions in condensed phase environments. To do so, we contrast Landauer with exact time-dependent non-equilibrium Green's function quantum transport computations in a two-site molecular junction subject to exponentially correlated noise. Under resonant transport conditions, we find Landauer accuracy to critically depend on intramolecular interactions. By contrast, under nonresonant conditions, the emergence of incoherent transport routes that go beyond Landauer depends on charging and discharging processes at the electrode-molecule interface. In both cases, decreasing the rate of charge exchange between the electrodes and molecule and increasing the interaction strength with the thermal environment cause Landauer to become less accurate. The results are interpreted from a time-dependent perspective where the noise prevents the junction from achieving steady-state and from a fully quantum perspective where the environment introduces dephasing in the dynamics. Using these results, we analyze why the Landauer approach is so useful to understand experiments, isolate regimes where it fails, and propose schemes to chemically manipulate the degree of transport coherence.