Relativistic millicharged particles ($chi_q$) have been proposed in various extensions to the Standard Model of particle physics. We consider the scenarios where they are produced at nuclear reactor core and via interactions of cosmic-rays with the earths atmosphere. Millicharged particles could also be candidates for dark matter, and become relativistic through acceleration by supernova explosion shock waves. The atomic ionization cross section of $chi_q$ with matter are derived with the equivalent photon approximation. Smoking-gun signatures with significant enhancement in the differential cross section are identified. New limits on the mass and charge of $chi_q$ are derived, using data taken with a point-contact germanium detector with 500g mass functioning at an energy threshold of 300~eV at the Kuo-Sheng Reactor Neutrino Laboratory.