We report NuSTAR observations of NuSTAR J033202-2746.8, a heavily obscured, radio-loud quasar detected in the Extended Chandra Deep Field-South, the deepest layer of the NuSTAR extragalactic survey (~400 ks, at its deepest). NuSTAR J033202-2746.8 is reliably detected by NuSTAR only at E>8 keV and has a very flat spectral slope in the NuSTAR energy band (Gamma=0.55^{+0.62}_{-0.64}; 3-30 keV). Combining the NuSTAR data with extremely deep observations by Chandra and XMM-Newton (4 Ms and 3 Ms, respectively), we constrain the broad-band X-ray spectrum of NuSTAR J033202-2746.8, indicating that this source is a heavily obscured quasar (N_H=5.6^{+0.9}_{-0.8}x10^23 cm^-2) with luminosity L_{10-40 keV}~6.4x10^44 erg s^-1. Although existing optical and near-infrared (near-IR) data, as well as follow-up spectroscopy with the Keck and VLT telescopes, failed to provide a secure redshift identification for NuSTAR J033202-2746.8, we reliably constrain the redshift z=2.00+/-0.04 from the X-ray spectral features (primarily from the iron K edge). The NuSTAR spectrum shows a significant reflection component (R=0.55^{+0.44}_{-0.37}), which was not constrained by previous analyses of Chandra and XMM-Newton data alone. The measured reflection fraction is higher than the R~0 typically observed in bright radio-loud quasars such as NuSTAR J033202-2746.8, which has L_{1.4 GHz}~10^27 W Hz^-1. Constraining the spectral shape of AGN, including bright quasars, is very important for understanding the AGN population, and can have a strong impact on the modeling of the X-ray background. Our results show the importance of NuSTAR in investigating the broad-band spectral properties of quasars out to high redshift.