The key is that the UDF's enqueue is transactional with the database update. Let's say the database update is inserting a new order. This provides the guarantee that if a new order is inserted, a job to process the order is also enqueued. It's impossible for a new order to be inserted without its processing job also being enqueued. Then the durable workflow/queue system is responsible for making sure the processing job, once enqueued, actually executes.
And if that job never runs? Or if that job runs and then fails to commit that it ran in postgres?