We present synthetic spectral energy distributions (SEDs) for single-age, single-metallicity stellar populations (SSPs) covering the full optical spectral range at moderately high resolution [full width at half-maximum (FWHM) = 2.3Å]. These SEDs constitute our base models, as they combine scaled-solar isochrones with an empirical stellar spectral library [Medium resolution INT Library of Empirical Spectra (MILES)], which follows the chemical evolution pattern of the solar neighbourhood. The models rely as much as possible on empirical ingredients, not just on the stellar spectra, but also on extensive photometric libraries, which are used to determine the transformations from the theoretical parameters of the isochrones to observational quantities. The unprecedented stellar parameter coverage of the MILES stellar library allowed us to safely extend our optical SSP SED predictions from intermediate- to very-old-age regimes and the metallicity coverage of the SSPs from super-solar to [M/H] = -2.3. SSPs with such low metallicities are particularly useful for globular cluster studies. We have computed SSP SEDs for a suite of initial mass function shapes and slopes. We provide a quantitative analysis of the dependence of the synthesized SSP SEDs on the (in)complete coverage of the stellar parameter space in the input library that not only shows that our models are of higher quality than those of other works, but also in which range of SSP parameters our models are reliable. The SSP SEDs are a useful tool to perform the analysis of stellar populations in a very flexible manner. Observed spectra can be studied by means of full spectrum fitting or by using line indices. For the latter, we propose a new line index system to avoid the intrinsic uncertainties associated with the popular Lick/IDS system and provide more appropriate, uniform, spectral resolution. Apart from constant resolution as a function of wavelength, the system is also based on flux-calibrated spectra. Data can be analysed at three different resolutions: 5, 8.4 and 14Å (FWHM), which are appropriate for studying globular cluster, low- and intermediate-mass galaxies, and massive galaxies, respectively. Furthermore, we provide polynomials to transform current Lick/IDS line index measurements to the new system. We provide line index tables in the new system for various popular samples of Galactic globular clusters and galaxies. We apply the models to various stellar clusters and galaxies with high-quality spectra, for which independent studies are available, obtaining excellent results. Finally, we designed a web page from which not only these models and stellar libraries can be downloaded but which also provides a suite of on-line tools to facilitate the handling and transformation of the spectra.