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As arcosine said, visible reflectivity is only part of the equation. In addition to visible light you also have to consider infrared and ultraviolet. Even the reflectivity of the whole light spectrum is only half the equation. The reflectivity of an object determines how quickly it absorbs heat. The other half is how quickly an object can radiate heat. This is called Emissivity. The scale is 0 to 1 with a larger number representing faster heat radiation. Chrome has an emissivity of about 0.05 to 0.1 while paint is about 0.90 to 0.95.
So chrome heats up slower but holds more heat because it cannot radiate very quickly. A real world example is a chromed metal bumper vs a painted metal bumper. Under the blazing afternoon sun the chrome bumper will be hotter to the touch than the painted bumper.
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