Due to the design of the product it is not possible have two different SPE URL’s.
The usage policy option does create a second URL on the desktop and can be used for another URL such as a secondary self-service site.
This can be configured within the SPE ADM template:
1. Group policy Manager
2. Select the GPO containing the ADM template
3. Right click and select “Edit”
4. Select Computer configuration | Administrative Templates |Classic Administrative Templates (ADM) | Generic Settings | Usage policy Settings
5. Enable and Configure “display the usage policy button (command link)”
6. Enable and Configure “Set default URL”
7. Enable and configure “Set name and URL for the usage policy button (command link) English” (see screen shot)
8. Perform a GPupdate /force
9. See the result (see screen shot)