To know how best to handle your scenario, it would be helpful if you could clarify what your goal is with the additional URL and if you are trying to use SP-initiated SSO or IDP-initiated SSO.
If you want to add multiple relay state URLs the app needs to be set up for SP-initiated SSO and the Relay State value in set in the Azure portal only takes effect when using IDP-initiated SSO flow. Since SAML only provides browser-based SSO and isn't supported for mobile apps, a second URL shouldn't be required since everything would happen in the browser (unless there's a particular reason you would want to redirect users to a different spot).
In order to add multiple (dynamic) RelayState URLs, your application needs to be set up to use SP-initiated SSO. The app needs to send the RelayState as a parameter in the SAML request so that Azure AD will return the same information in the SAML response.
See Enable single sign-on with SAML for more details.
Since the RelayState is optional, if you just want to redirect the user after sign-in from the Azure side, you can add multiple reply URLs. To do this, you can go to the Single sign-on section and add the URL as a reply URL in the Reply URL (Assertion Consumer Service URL) field.
Let me know if you have further questions.
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