Molecular dynamics simulation results on hydrogen bonding in mixtures of methanol with CO2 at supercritical, liquid-like conditions are compared to H-1 NMR spectroscopic data that have recently become available. The molecular models are parametrized using vapor-liquid equilibrium data only, which they reliably describe. A new molecular model for methanol of Lennard-Jones plus point charge type is presented. This molecular methanol model is investigated in terms of its capability to yield hydrogen-bonding statistics. Simple assumptions are made regarding the assignment of NMR chemical shifts to the different types of hydrogen-bonded species. Only two state-independent parameters are fitted to the large NMR data set on the basis of hydrogen-bonding statistics from molecular simulations. Excellent agreement between the molecular simulation results and the NMR data is found. This shows that the molecular models of the simple type studied here cannot only describe thermodynamic properties but also structural effects of hydrogen bonding in solutions.