Probably your best port of call would be the PSE website, the leader and certainly the most popular of the grading services. They have a series of articles that explain how they grade stamps, with pictures of various grades etc. Some grading is based on centring alone, however the PSE numeric grade combines centring, soundness and eye appeal (to a lesser extent.) But you can read all about that on their site
http://www.psestamp.com/Intro.chtmlThis should give you a good idea on how to judge the quality of a stamp, however the average collector and even experienced philatelist will not be able to come up with a numeric grade. You just couldn't hope to have the market research and expertise to do it. What you should aim for is to be able to determine if a stamp is extra fine, very fine etc, and that takes a lot of experience.
There is a program that will come up with a centring grade for you using a scan of the stamp, however I cannot attest to it's accuracy. I've purchased stamps online that have had a printed "certificate" from this Ezgrader and they appear to at least fall within the bounds of the grade. I think it's an add-on program and you need to buy the inventory software Ezstamp, although I'm not 100% sure on that.
The grade and condition of a stamp is critical to it's value, so it's important that you learn about it. You'll often see stamps online with a CV listed in the title - that will be the CV for a Very Fine stamp, which is what Scott lists in their standard catalogues. Of course the stamp you then look at will often be nothing like very fine, and if you can't recognise that you may think you're getting a great deal when in fact you're getting something worth far less. So it's great to see you interested in this. Knowledge is important to a collector.
Balf