Dynamical decoupling (DD) is a powerful method for controlling arbitrary open quantum systems. In quantum spin control, DD generally involves a sequence of timed spin flips (π rotations) arranged to either average out or selectively enhance coupling to the environment. Experimentally, errors in the spin flips are inevitably introduced, motivating efforts to optimize error-robust DD. Here we invert this paradigm: by introducing particular control “errors” in standard DD, namely, a small constant deviation from perfect π rotations (pulse adjustments), we show we obtain protocols that retain the advantages of DD while introducing the capabilities of quantum state readout and polarization transfer. We exploit this nuclear quantum state selectivity on an ensemble of nitrogen-vacancy centers in diamond to efficiently polarize the 13C quantum bath. The underlying physical mechanism is generic and paves the way to systematic engineering of pulse-adjusted protocols with nuclear state selectivity for quantum control applications.