Enhanced Raman scattering from plasmonic nanostructures associated with surface enhanced (SERS) and tip enhanced (TERS) is seeing a dramatic increase in applications from bioimaging to chemical catalysis. The importance of gap-modes for high sensitivity indicates plasmon coupling between nanostructures plays an important role. However, the observed Raman scattering can change with different geometric arrangements of nanoparticles, excitation wavelengths, and chemical environments; suggesting differences in the local electric field. Our results indicate that molecules adsorbed to the nanostructures are selectively enhanced in the presence of competing molecules. This selective enhancement arises from controlled interactions between nanostructures, such as an isolated nanoparticle and a TERS tip. Complementary experiments suggest that shifts in the vibrational frequency of reporter molecules can be correlated to the electric field. Here we present a strategy that utilizes the controlled formation of coupled plasmonic structures to experimentally measure both the magnitude of the electric fields and the observed Raman scattering.