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The improvement in color in the second photo is probably due to having the correct white balance setting for the lighting situation you were in. Polarizers only remove glare and don't correct for color.
The first photo looks like you had an incorrect white balance setting. Blue skintones like that can occur if your white balance is set for sunlight but you're outdoors in the shade, for example. Keeping the white balance setting the same but moving the painting into full sun might be what gave you the warmer colors in the second shot.
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