Conventional radar and communication signals face challenges when integrating for accurate sensing in dense electromagnetic environments, especially in scenarios involving high-velocity targets estimation. To address this issue, we propose the random frequency agile-orthogonal frequency division multiplexing-based radar and communication (RFA-OFDM-based RadCom) signal, a novel framework that combines RFA hopping radar signal and OFDM signal. This framework effectively handles high-velocity Doppler scenarios, enhancing electronic countermeasure capabilities. In high-velocity scenarios, achieving accurate range and velocity estimation is crucial. We introduce a comprehensive received signal model that considers intrapulse and intersubcarrier Doppler effects, often overlooked in traditional high-velocity contexts. The proposed two-phase hierarchical perceptual methodology enables joint super-resolution estimation using the shared signal. We transform the shared signal echo model into a uniform linear array-like model and employ the matrix decomposition algorithm based on bidirectional weighted frequency smoothing (BWFS-MD) for decoherence processing. Subsequently, the estimation of signal parameters via rotational invariance techniques (ESPRIT)-complementary integrated subspace fitting (E-CISF) algorithm accurately estimates joint range and velocity. Meanwhile, the contrastive analysis of the mutual impacts between radar and communication functions is conducted. Theoretical analysis and simulation results robustly validate the superior performance of the proposed BWFS-MD algorithm. Furthermore, considering the precision of joint range-velocity estimation, real-time constraints, and super-resolution capability (which is emphasized), the E-CSIF algorithm demonstrates the best overall performance from a comprehensive perspective.