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As for how they measure the calories: they literally burn the food, then measure the heat released.
This is the main fallacy in calorie-counting. Wood, for goodness sake releases calories. But you, a human, can't absorb nourishment or calories from wood. You're not equipped to break wood down.
By the same token, burning a potato or an apple or banana may well release more calories in heat than your body could ever liberate from the same fruit from the digestive process. So it's not just about calories, but about how easily the calories in a particular food are absorbed by the body. And this varies a lot.
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