In the near future, we will be able to search for life on transiting terrestrial exoplanets using extremely large ground-based telescopes (ELTs). Their ability to access the visible and near infrared wavelengths, where the O2 bands are prominent, will complement the James Webb Space Telescope’s strength in longer wavelength molecule detection. Ground-based telescopes capable of high-resolution spectroscopy are crucial for detecting O2, but using them to detect other environmental molecules or alternative biosignatures has not been fully explored. Although O2 is the most readily detectable biosignature on an Earth-like world for high-resolution observations, it must always be interpreted in the context of its planetary environment due to the possibility of abiotic generation. This context may include the presence of other molecules that can point to a habitable environment, or that can strengthen its interpretation as being more likely to be produced by life. To better understand the accessibility of environmental context using ground-based telescopes, we simulated high-resolution observations of Archean and pre-industrial Earth atmospheres transiting a range of M-dwarf hosts, ensuring photochemical consistency with each host star’s spectral type. These simulations included explicit treatment of telescope, instrument, detector, and telluric effects to model realistic signal-to-noise values in high-resolution spectra. Using the cross-correlation technique, we then determined the detectability of O2, O3, CH4, CO2, CO, and H2O in these atmospheres. We match the near-infrared O2 detectability calculations of previous studies, and show that CH4 and CO2 are potentially accessible for very nearby systems. However, for an Earth-like atmosphere in the TRAPPIST-1 system, we were unable to detect CH4 and CO2 above a three-sigma level within a reasonable number of transits. Molecule detectability is broadly dependent on spectral type, but could also be strongly influenced by other host star properties such as luminosity and size. Our study demonstrates that the upcoming ELTs may play a major role in terrestrial exoplanet characterization beyond O2 detection, and our results can inform molecule and target prioritization for observers in the near future.