A quantum computer requires systems that are isolated from their environment, but can be integrated into devices, and whose states can be measured with high accuracy. Nuclear spins in solids promise long coherence lifetimes, but they are difficult to initialize into known states and to detect with high sensitivity. We show how the distinctive optical properties of enriched (28)Si enable the use of hyperfine-resolved optical transitions, as previously applied to great effect for isolated atoms and ions in vacuum. Together with efficient Auger photoionization, these resolved hyperfine transitions permit rapid nuclear hyperpolarization and electrical spin-readout. We combine these techniques to detect nuclear magnetic resonance from dilute (31)P in the purest available sample of (28)Si, at concentrations inaccessible to conventional measurements, measuring a solid-state coherence time of over 180 seconds.