Sampling-based Model Predictive Control (MPC) has been a practical and effective approach in many domains, notably model-based reinforcement learning, thanks to its flexibility and parallelizability. Despite its appealing empirical performance, the theoretical understanding, particularly in terms of convergence analysis and hyperparameter tuning, remains absent. In this paper, we characterize the convergence property of a widely used sampling-based MPC method, Model Predictive Path Integral Control (MPPI). We show that MPPI enjoys at least linear convergence rates when the optimization is quadratic, which covers time-varying LQR systems. We then extend to more general nonlinear systems. Our theoretical analysis directly leads to a novel sampling-based MPC algorithm, CoVariance-Optimal MPC (CoVo-MPC) that optimally schedules the sampling covariance to optimize the convergence rate. Empirically, CoVo-MPC significantly outperforms standard MPPI by 43-54% in both simulations and real-world quadrotor agile control tasks. Videos and Appendices are available at \url{https://lecar-lab.github.io/CoVO-MPC/}.