If you develop a .NET based application, Microsoft provides a library called WIF, which is used to communicate with the AD FS in a +- comfortable way (configuration + little code adaptations to get the claims from the authentication message provided by the AD FS).
There are few protocols that both AD FS 2.0 and WIF support, to make the SSO work, the most common ones are (afaik) SAML 2.0 and WS-Federation. Both are built on XML messages, but you are not required to know the details, if you use WIF.
For WS - Federation, the WIF library provides a plugin for Visual Studio, which allows you to configure your site as the relying party with your AD FS.
You CAN use the credentials within your DB to identify users, you can actually customize AD FS's entire login page and authentication events. However the basic installation requires each user to be defined within your Active Directory. You can also use your DB as a claims store (another data base AD FS will use to provide the relying applications with information about users). Note that if you intend to use an AD behind the AD FS, your AD FS service must be able to access it and LDAP query it, which I'm not sure will work for you, if your users login to their local domain that the AD FS is not familiar with.
IF you are not required to support industry SSO standard protocols (SAML 2.0 I've mentioned), I'm not sure implementing AD FS will be such a good solution. It forces you to work in a certain way, which is not always that comfortable.