Recent progress in achieving high degrees of monodispersity in chemical synthesis of complex nanostructures creates the unique situation in which individual nanostructures become representative for the whole ensemble. Under these conditions, atomistic simulations can play a completely new role in interpreting structural data obtained from averaging techniques. We apply this approach to fivefold twinned Ag nanowires for which the existence of an ambient-stable tetragonal phase in the nanowire core has been recently proposed. Quantitative comparison of experimental X-ray diffraction data with atomistic calculations unequivocally shows that the diffractograms can be fully explained by the complex strain state and defect structure of fivefold twinned Ag nanowires with fcc crystal structure. In addition, our approach enables rapid and accurate determination of wire diameters by a modified Scherrer analysis which uses a database generated by atomistic simulations.