A “smart contract” is basically an ordinary payment contract where execution steps are gated by separate semaphore controlled by sunsets of the participant set.
What can you do with that? It’s hard to answer without being so general as to be useless, or without getting too specific such that we lose the big picture.
“Block chain” is about replacing courts and arbitration with a computer network, and replacing contract lawyers with programmers. What makes this possible is the fair, untrusted, equal access semaphore a bitcoin spend provides.