We study the metastability and decay of multiply-charged superflow in a ring-shaped atomic Bose-Einstein condensate. Supercurrent corresponding to a giant vortex with topological charge up to q=10 is phase-imprinted optically and detected both interferometrically and kinematically. We observe q=3 superflow persisting for up to a minute and clearly resolve a cascade of quantised steps in its decay. These stochastic decay events, associated with vortex-induced $2 pi$ phase slips, correspond to collective jumps of atoms between discrete q values. We demonstrate the ability to detect quantised rotational states with > 99 % fidelity, which allows a detailed quantitative study of time-resolved phase-slip dynamics. We find that the supercurrent decays rapidly if the superflow speed exceeds a critical velocity in good agreement with numerical simulations, and we also observe rare stochastic phase slips for superflow speeds below the critical velocity.
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