We study methods based on reproducing kernel Hilbert spaces for estimating the value function of an infinite-horizon discounted Markov reward process (MRP). We study a regularized form of the kernel least-squares temporal difference (LSTD) estimate; in the population limit of infinite data, it corresponds to the fixed point of a projected Bellman operator defined by the associated reproducing kernel Hilbert space. The estimator itself is obtained by computing the projected fixed point induced by a regularized version of the empirical operator; due to the underlying kernel structure, this reduces to solving a linear system involving kernel matrices. We analyze the error of this estimate in the $L^2(μ)$-norm, where $μ$ denotes the stationary distribution of the underlying Markov chain. Our analysis imposes no assumptions on the transition operator of the Markov chain, but rather only conditions on the reward function and population-level kernel LSTD solutions. We use empirical process theory techniques to derive a non-asymptotic upper bound on the error with explicit dependence on the eigenvalues of the associated kernel operator, as well as the instance-dependent variance of the Bellman residual error. In addition, we prove minimax lower bounds over sub-classes of MRPs, which shows that our rate is optimal in terms of the sample size $n$ and the effective horizon $H = (1 - γ)^{-1}$. Whereas existing worst-case theory predicts cubic scaling ($H^3$) in the effective horizon, our theory reveals that there is in fact a much wider range of scalings, depending on the kernel, the stationary distribution, and the variance of the Bellman residual error. Notably, it is only parametric and near-parametric problems that can ever achieve the worst-case cubic scaling.