If you assigned the Twilio number to the user but SMS is still sending from the old default Twilio number instead of the Twilio number assigned to the user, please make sure you are login as the user to test SMS.
When sending an SMS to a contact we always get the User who is Logged In to be used as the Sender, we do that because even though the Contact may be Assigned to someone else, the specific User that is there might be talking about something else, or have a different approach, therefore they will want to use their own number to get replies to.
If the user login has no Twilio number assigned, we will use the default Twilio number in the location.