Overexposing and pulling the exposure back in post-processing was the standard method for the Kodak 14n camera. It was "the" way to shoot that camera in RAW mode among the commercial and portrait shooters who adopted that camera. It was/is a good method.
I have done it with the Canon 5D as well. One of the issues about what KmH and Christie Photo were talking about was was actually constitutes "over-exposure"; for example, the blinkies and the histogram you see in the camera are derived from the JPEG image that resides inside the RAW file; unless you have what is called a "Uni-White Balance" or a "Near-Uni-White Balance" loaded into your camera (unlikely), the overexposure warning lights aka the blinkies, as showing ovrexposure on an image that has had some kind of a tone curve applied to it. Soooooo, if you have the camera set to a Picture Style or Custom Option like say "Direct Print", or "Vivid", or "Faithful", or "Portrait Mode 1 or 2" and so on, the blinkies will be applied based on how the RAW data is interpreted in THE JPEG IMAGE FILE, WITH a TONE CURVE applied.
A RAW capture with a Normal or Standard Tone Curve will look like a decent image when opened in Photoshop, or when viewed on the camera's LCD screen. The shadows will be set so they look darkish, there will be a large swath of midtone values that all look decent, and the highlights will be set more or less correctly. So, the "blinkies" and the histogram will tend to show that the sensor has reached saturation or full-well capacity at an exposure that is actually *less* than what the sensor could accept if the data were mapped out in a linear form.
So...like Thom Hogan has been saying about the new Nikon D7000: newbies shoot images with it, and say that the D7000 is overexposing; he notes that what the camera is doing is over-DEVELOPING the image data, and that if the user simply lowers the tone curve/saturation in the camera, then the camera's exposure system is almost perfect. So, in short, yes, there is a way of quote "over-exposing" and then pulling the exposure BACK as they say, in post processing, and it can yield very good results,if you know what you are doing,