The electric quadrupole moment of 49Sc was measured by collinear laser spectroscopy at CERN-ISOLDE to be Qs=−0.159(8) eb, and a nearly tenfold improvement in precision was reached for the electromagnetic moments of 47,49Sc. The single-particle behavior and nucleon-nucleon correlations are investigated with the electromagnetic moments of Z=21 isotopes and N=28 isotones as valence neutrons and protons fill the distinctive 0f7/2 orbit, respectively, located between magic numbers, 20 and 28. The experimental data are interpreted with shell-model calculations using an effective interaction, and ab-initio valence-space in-medium similarity renormalization group calculations based on chiral interactions. These results highlight the sensitivity of nuclear electromagnetic moments to different types of nucleon-nucleon correlations, and establish an important benchmark for further developments of theoretical calculations.