Chromium-based superalloys are considered for the heat exchanger tubes in next generation concentrated solar power operating at ~800 °C. Unlike the Ni based γ-γ’ superalloys, where the properties are governed by cuboidal γ’ precipitates embedded in the γ matrix, Cr-superalloys comprise a disordered-bcc Cr matrix reinforced with highly coherent ordered-bcc NiAl precipitates, that exhibit spherical shapes due to their interaction at the Cr matrix-NiAl precipitate interface. Though Cr based superalloys offer some superior properties compared to Ni based superalloys, improvement of their mechanical properties at room temperature is still required, which can be achieved through alloying the Cr-NiAl-X system with elements X such as Fe, Si, Ti or Ag. In this work, first-principles density functional theory simulations are employed to gain quantum level understanding on the interaction at the Cr-NiAl interface and, consequently, to understand the NiAl precipitate nucleation and growth. Investigations of segregation of alloying elements in the Cr-NiAl-X system, and their effects on the interface energetics are performed, which allows for the identification of suitable alloying elements to tailor the properties of the Cr-NiAl-X system to meet the design targets for thermal stability, strength and ductility. The first-principles simulations are compared to experimentally measured atom probe tomography images and precipitate coarsening kinetics. In addition to understanding NiAl precipitate formation, these first-principles simulations provide a guideline for the identification of suitable alloying elements to tailor the properties of the Cr-NiAl-X superalloy, ultimately leading to the improved room temperature ductility and so enable their application in next generation concentrated solar power.