We present investigations of radio-frequency (RF) resonances observed in an optically pumped rubidium vapor. By measuring the systematic shifts (the Bloch–Siegert shifts) of RF resonances in low magnetic fields, we demonstrate limitations of the rotating-wave approximation in the case of angular momentum . The resonance shifts and deformations are characterized in a wide range of parameters and it is shown that the observed behavior is far more complex than in a standard two-level system. It is also demonstrated that the shifts can be controllably turned on or off by switching between the oscillating and rotating magnetic field. Experimental results are supported with numerical calculations, reproducing all features of the observed signals. Besides fundamental aspect of the research, application of rotating magnetic field helps to suppress/evaluate spectroscopic-measurement and precise-metrology systematic errors. The reported study has also important implications for quantum metrology and information processing beyond RWA and standard two-state qubit dynamics.