We derive formulas for the first- and higher-order derivatives of the steady state performance measures for changes in transition matrices of irreducible and aperiodic Markov chains. Using these formulas, we obtain a Maclaurin series for the performance measures of such Markov chains. The convergence range of the Maclaurin series can be determined. We show that the derivatives and the coefficients of the Maclaurin series can be easily estimated by analysing a single sample path of the Markov chain. Algorithms for estimating these quantities are provided. Markov chains consisting of transient states and multiple chains are also studied. The results can be easily extended to Markov processes. The derivation of the results is closely related to some fundamental concepts, such as group inverse, potentials, and realization factors in perturbation analysis. Simulation results are provided to illustrate the accuracy of the single sample path based estimation. Possible applications to engineering problems are discussed.