Earlier studies of the velocity distributions of heavy-Rydberg ion-pair states formed in collisions between potassium Rydberg atoms with low-to-intermediate values of n, 10 ≲ n ≲ 15, and targets that attach free low-energy electrons have shown that such measurements can provide a window into the dynamics of dissociative electron capture. Here we propose that the reaction dynamics can be explored in much greater detail through studies using hyperthermal Rydberg atoms. This is demonstrated using, as an example, helium Rydberg atoms and a semi-classical Monte Carlo collision code developed specifically to model the dynamics of Rydberg electron transfer in collisions between Rydberg atoms and attaching targets. The simulations show that the outcome of collisions is sensitive not only to the lifetime and decay energetics of the excited intermediate negative ion formed upon initial Rydberg electron capture but also to the radial electron probability density distribution in the Rydberg atom itself, i.e., to its ℓ value.