Can I use an existing user as Django admin when enabling admin for the first time?
Yes, but you'll do it through the Django shell:
python manage.py shell
Then fetch your user from the database:
from django.contrib.auth.models import User
user = User.objects.get(username="myname")
user.is_staff = True
user.is_admin = True
user.save()
Exit the shell, and that user will now be an admin user.
You can also add the line
user.is_superuser = True
before calling user.save()
if you want or need this user to be a superuser and have all the available permissions.