We performed the largest and most homogeneous spectroscopic survey of field RR Lyraes (RRLs). We secured ≍6300 high-resolution (HR, R ∼ 35,000) spectra for 143 RRLs (111 fundamental, RRab; 32 first-overtone, RRc). The atmospheric parameters were estimated by using the traditional approach and the iron abundances were measured by using an LTE line analysis. The resulting iron distribution shows a well-defined metal-rich tail approaching solar iron abundance. This suggests that field RRLs experienced a complex chemical enrichment in the early halo formation. We used these data to develop a new calibration of the ΔS method. This diagnostic, based on the equivalent widths of Ca II K and three Balmer (Hδ,γ,β) lines, traces the metallicity of RRLs. For the first time, the new empirical calibration: (i) includes spectra collected over the entire pulsation cycle; (ii) includes RRc variables; (iii) relies on spectroscopic calibrators covering more than three dex in iron abundance; and (iv) provides independent calibrations based on one/two/three Balmer lines. The new calibrations were applied to a data set of both SEGUE-SDSS and degraded HR spectra totalling 6451 low-resolution (R ∼ 2000) spectra for 5001 RRLs (3439 RRab, 1562 RRc). This resulted in an iron distribution with a median η = -1.55 ± 0.01 and σ = 0.51 dex, in good agreement with literature values. We also found that RRc are 0.10 dex more metal-poor than RRab variables, and have a distribution with a smoother metal-poor tail. This finding supports theoretical prescriptions suggesting a steady decrease in the RRc number when moving from metal-poor to metal-rich stellar environments. * Based on observations obtained with the du Pont telescope at Las Campanas Observatory, operated by Carnegie Institution for Science. Based in part on data collected at Subaru Telescope, which is operated by the National Astronomical Observatory of Japan. Based partly on data obtained with the STELLA robotic telescopes in Tenerife, an AIP facility jointly operated by AIP and IAC. Some of the observations reported in this paper were obtained with the Southern African Large Telescope (SALT). Based on observations made with the Italian Telescopio Nazionale Galileo (TNG) operated on the island of La Palma by the Fundación Galileo Galilei of the INAF (Istituto Nazionale di Astrofisica) at the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere.