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Plastic scratches over time and decreases visibility. Glass in side windows and back glass is tempered for safety (breaks into small cubes) more durable to the elements. Plastic will break with sharp, jagged pieces. Windshield is a laminate with a plastic sheet between two panes of glass to help hold the pieces in place in case of accident.
EDIT: In most states in the US, it is illegal, for above reasons, to replace a broken car windshield with plastic. Most plastics will also dull and color in the sun; glass won't.
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