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Who administers the blood withdrawal?
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In my area, its done at a hospital, by medical professionals, with officers in attendance to do chain of custody.
If you are stopped for suspicion of DUI, you get the breathalyzer. If you are involved in an accident, you get the blood test.
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Why do they need blood samples? Why won't a breathalyzer be sufficient to find drunk drivers?
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because there are several things that will give a false positive on the breath test. Like mouthwashes or cough syrup with alcohol in them.
The blood test results (BAC) are very difficult to argue against in court, AND there is no issue about the calibration/accuracy of the breath meter, and, the chain of custody tracking, including the time of the sample allows for a legally acceptable standard. Alcohol in the blood breaks down at a given rate, so a sample taken 1 hour (for example) after the accident can be used to give an accurate base for what was in the blood at the time of the accident.
That's why they take blood samples.