You'll get better results with a scanner than with a camera. But if you're set on using your camera, here're a few suggestions.
Use a copy stand if you have one.
You want the photo flat. Use a piece of plate glass if needed to keep the corners from curling up.
Have the sensor parallel to the photo, otherwise you'll get distortion.
You don't want your camera too close to the photo, but that's going to depend on the size of the original. Thus you may or may not have to use the macro mode.
You want even lighting. You don't want the light brighter on one part of the photo than on another. This also means you don't want the camera (or its support) casting a shadow onto the photo. You don't want to use the built-in flash, since it won't give you even lighting.
You also want a good stable support for the camera. Use the self-timer (or a remote control) so as not to shake the camera with the shutter press.
If you have the negatives, you're better off taking them to a photo store and having them scan them onto a CD or DVD. Or, if you have a lot of prints, many photo stores will do scan entire shoe box full of prints for a reasonable price.
Testimonial: "This was very helpful but I still need to now the exact camera settings to use."
Unfortunately, I can't give you the exact settings, since I don't know the exact circumstances. What kind of light are you using? Where is it coming from?
If the camera is on a tripod or other stable platform, I'd start with Av mode and stop the aperture down to f/8 or smaller to maximize depth of field. I'd take a few shots and examine them. That would tell me whether I had adequate depth of field and lighting.
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