Electron impact ionization of a helium atom in a helium nanodroplet is followed by rapid charge migration, which can ultimately result in the localization of the charge on an atomic or molecular solute. This process is studied here for the cases of hydrogen cyanide, acetylene, and cyanoacetylene in helium, using a new experimental method we call optically selected mass spectrometry (OSMS). The method combines infrared laser spectroscopy with mass spectrometry to separate the contributions to the overall droplet beam mass spectrum from the various species present under a given set of conditions. This is done by vibrationally exciting a specific species that exists in a subset of the droplets (for example, the droplets containing a single HCN molecule). The resulting helium evaporation leads to a concomitant reduction in the ionization cross sections for these droplets. This method is used to study the charge migration in helium and reveals that the probability of charge transfer to a solvated molecule does not approach unity for small droplets and depends on the identity of the solvated molecule. The experimental results are explained quantitatively by considering the effect of the electrostatic potential (between the charge and the embedded molecule) on the trajectory of the migrating charge.