Polymer electrolytes typically exhibit diminished ionic conductivity due to the presence of correlation effects between the cations and anions. Microscopically, transient ionic aggregates, e.g., ion-pairs, ion-triplets, or higher order ionic clusters, engender ionic correlations. Employing all-atom simulation of a model polymer electrolyte comprising of poly(ethylene oxide) and lithium iodide, the ionic correlations are explored through construction of elementary functions between pairs of the ionic species that qualitatively explains the spatio-temporal nature of these correlations. Furthermore, commencing from the exact Einstein-like equation describing the collective diffusivity of the ions in terms of the average diffusivity of the ions (i.e., the self-terms) and the correlations from distinct pairs of ions, several phenomenological parameters are introduced to keep track of the simplification procedure that finally boils down to the recently proposed phenomenological model by Stolwijk and Obeidi (SO) [Stolwijk, N. A.; Obeidi, S. Phys. Rev. Lett. 2004, 93, 125901]. The approximation parameters, which can be retrieved from simulations, point to the necessity of additional information in order to fully describe the correlation effects apart from the mere fraction of ion-pairs that apparently accounts for the correlations originating from only the nearest neighbor structural correlations. These parameters are close to, but are not exactly unity, as assumed in the SO model. Finally, as an application of the extended SO model, one is able to estimate the dynamics of the free and non-free ions as well as their fractions from the knowledge of the single particle diffusivities and the collective diffusivity of the ions.