Toad currently does not have a functionality to designate an Active Toad for Oracle (TFO) key (in a license key file that has multiple TFO keys) during license key deployment across different users in a network.
As a suggestion, create two ProductLicenses.xml files on the network: one with the first key and one with the second key. Then, create two login scripts on the network: one that copies the first xml file to the user’s computer, and another one that copies the second xml file. Then, on the domain controller, you can specify the login script to run for each user each time that user logs in. For the users you want to have i.e. an Xpert license key, you can choose the login script that copies the ProductLicenses.xml file that contains the Xpert license key. For the other users, you can choose the login script that copies the other ProductLicenses.xml file. The advantage of this is even if users somehow finds a way to change their key to gain additional functionality, it will be reset back to the default key once the user logs back into the network.
Alternatively, if you just want to deploy two different TFO keys across different users, you can create a batch file and a ProductLicenses.xml file (one set for each TFO key), and run one batch file for i.e. Toad Xpert users and the other batch file for i.e. Toad Pro users in your network.