We present initial results of a deep near-IR spectroscopic survey covering the 15 fields of the Keck Baryonic Structure Survey (KBSS) using MOSFIRE on the Keck 1 telescope, focusing on a sample of 251 galaxies with redshifts 2.0< z < 2.6, star-formation rates 2 < SFR < 200 M_sun/yr, and stellar masses 8.6 < log(M*/M_sun) < 11.4, with high-quality spectra in both H- and K-band atmospheric windows. We show unambiguously that the locus of z~2.3 galaxies in the BPT nebular diagnostic diagram exhibits a disjoint, yet similarly tight, relationship between the ratios [NII]6585/Halpha and [OIII]/Hbeta as compared to local galaxies. Using photoionization models, we argue that the offset of the z~2.3 locus relative to z~ 0 is explained by a combination of harder ionizing radiation field, higher ionization parameter, and higher N/O at a given O/H than applies to most local galaxies, and that the position of a galaxy along the z~2.3 star-forming BPT locus is surprisingly insensitive to gas-phase oxygen abundance. The observed nebular emission line ratios are most easily reproduced by models in which the net ionizing radiation field resembles a blackbody with effective temperature T_eff = 50000-60000 K and N/O close to the solar value at all O/H. We critically assess the applicability of commonly-used strong line indices for estimating gas-phase metallicities, and consider the implications of the small intrinsic scatter in the empirical relationship between excitation-sensitive line indices and stellar mass (i.e., the mass-metallicity relation), at z~2.3.