To expand on nzpcmad's answer, you can set up Claims Provider trusts other than Active Directory in the ADFS Management console under Trust Relationships > Claims Provider Trusts, they effectively chain ADFS with custom STS services.
The entries you add will be added to the Home Realm discovery page within the ADFS web site, such that authenticating users will be presented with a drop-down list to essentially choose the Claims Provider they wish to be authenticated against.
Automatic sign-in will still work for internal users who choose your Active Directory (ADFS provider), whilst members of other Providers will be redirected to their chosen Claims Provider's web site, which will typically present a Forms login page and authenticate against a back-end membership database, all external users (who are not able to present an NTLM or Kerberos token will be required to enter their details - for AD users this will mean they have to enter their domain\user string (or user@domain) and internal password.
Of course, you have to create these providers yourself, in the old WIF days this meant using the fairly clunky Custom STS template, however you can now streamline the procedure with a simple OWIN-based MVC5 site. Alternatively, as nzpcmad suggests, you could look at using IdentityServer.