We examine the effects of impurities (doping) and rotational excitation on the structural and energetic properties of helium clusters. Quantum Monte Carlo (QMC) techniques are used to study ground and rotationally excited states of pure and doped clusters. We use exponentially correlated wave functions and treat the molecular impurities as rigid. Whereas pure He_N show essentially monotonic decay of density from a central maximum value, addition of impurities induces local ordering of He to an extent dependent on the impurity-He binding. Rotational excitation of He_N gives rise to extremely large centrifugal distortions. The location of impurities also appears to change upon rotational excitation. The implications of these distortions on impurity spectra are discussed for SF₆He_N, and compared to recent experimental results.