A recent study of the interaction of a lithium atom with the thiophene molecule found a large disagreement between high-level coupled duster (CCSD(T)/AVTZ) and quantum Monte Carlo (fixed-node diffusion Monte Carlo, or FNDMC) calculations. We address this "lithium-thiophene riddle" by analyzing the influence of crucial FNDMC simulation parameters, namely, the one-electron models, basis sets, and pseudopotentials used for the generation of the trial wave function. These are shown to have a significant impact on the calculated FNDMC interaction energies, and good agreement between CCSD(T) and FNDMC is found when nodal hypersurfaces of sufficient quality are used. On the basis of our proposed consensus reference value, we go on to benchmark the standard toolbox of lower-level quantum chemistry methods for this model interaction. Newly developed dispersion-corrected DFT methods perform reasonably well despite the partial charge transfer character of the interaction and might well be worthy of further study in larger lithium-thiophene systems.