The more blocks on the inside of the Smeltery, the more slots there are available to use.
By default, melting ores will give you two ingots' worth of molten metal, effectively doubling your ores. Some modpacks may have this disabled.
Certain combinations of molten metals will create alloys. If two molten metals that are in a Smeltery can alloy together, they will, so be careful what metals you put into a Smeltery at the same time.
One part Gold and one part Silver will alloy into two parts Electrum.
Newly molten metals will go to the top of the stack, and things at the bottom are cast first. You can click a molten metal to send it to the bottom so you can cast it.
To make a Cast, make a tool part out of a cheap material you don't mind losing and place it in the Casting Table. Melt 2 ingots of Gold or 1 ingot of Aluminium Brass and then right click the Faucet to pour the molten metal onto the tool part. This will create a reusable Cast for metal parts, destroying the tool part you used in the process.
You can do the same thing with 2 Clay balls to make a Clay Cast, which breaks after one use but is much cheaper.
To make a metal tool part, place a Cast into the Casting Table and activate the Faucet, and the molten metal will pour into the Cast and harden. Right click the Casting Table again to take out the metal tool part.