Radiative cooling is a passive cooling technology that offers great promises to reduce space cooling cost, combat the urban island effect and alleviate the global warming. To achieve passive daytime radiative cooling, current state-of-the-art solutions often utilize complicated multilayer structures or a reflective metal layer, limiting their applications in many fields. Attempts have been made to achieve passive daytime radiative cooling with single-layer paints, but they often require a thick coating or show partial daytime cooling. In this work, we experimentally demonstrate remarkable full daytime sub-ambient cooling performance with both BaSO4 nanoparticle films and BaSO4 nanocomposite paints. BaSO4 has a high electron bandgap for low solar absorptance and phonon resonance at 9 um for high sky window emissivity. With an appropriate particle size and a broad particle size distribution, BaSO4 nanoparticle film reaches an ultra-high solar reflectance of 97.6% and high sky window emissivity of 0.96. During field tests, BaSO4 film stays more than 4.5C below ambient temperature or achieves average cooling power of 117 W/m2. BaSO4-acrylic paint is developed with 60% volume concentration to enhance the reliability in outdoor applications, achieving solar reflectance of 98.1% and sky window emissivity of 0.95. Field tests indicate similar cooling performance to the BaSO4 films. Overall, our BaSO4-acrylic paint shows standard figure of merit of 0.77 which is among the highest of radiative cooling solutions, while providing great reliability, the convenient paint form, ease of use and the compatibility with commercial paint fabrication process.