We examine the absorption line spectra of a sample of 31 luminous (M_UV=-23) Lyman break galaxies at redshift z~6 using data taken with the FOCAS and OSIRIS spectrographs on the Subaru and GTC telescopes. For two of these sources we present longer exposure data taken at higher spectral resolution from ESOs X-shooter spectrograph. Using these data, we demonstrate the practicality of stacking our lower resolution data to measure the depth of various interstellar and stellar absorption lines to probe the covering fraction of low ionization gas and the gas-phase and stellar metallicities near the end of the era of cosmic reionization. From maximum absorption line depths of SiII1260 and CII1334, we infer a mean covering fraction of >0.85+/-0.16 for our sample. This is larger than that determined using similar methods for lower luminosity galaxies at slightly lower redshifts, suggesting that the most luminous galaxies appear to have a lower escape fraction than fainter galaxies, and therefore may not play a prominent role in concluding reionization. Using various interstellar absorption lines we deduce gas-phase metallicities close to solar indicative of substantial early enrichment. Using selected stellar absorption lines, we model our spectra with a range of metallicities using techniques successfully employed at lower redshift and deduce a stellar metallicity of 0.4 +0.3/-0.1 solar, consistent with the stellar mass - stellar metallicity relation recently found at z~3-5. We discuss the implications of these metallicity estimates for the typical ages of our luminous galaxies and conclude our results imply initial star formation at redshifts z~10, consistent with independent analyses of earlier objects.