Sure. The first big difference is guilds. Dwarves have different guilds, and members of those guilds learn certain skills twice as fast. You starting seven might start out as guild members, so it pays to do the "prepare carefully" option at the beginning. If, for example, you get a mason's guild dwarf, give him masonry skills. Later on, you can build a guild hall, and have dwarves join and leave guilds. There is also a garrison, which is like the guild hall, but for military guilds: guards (good on defense) legionnaires (melee) marksmen (shooty things) and wrestlers (speed). Military, guilds, sorcerers, and priests are mutually exclusive, a dwarf can only be a member of one.
By default, dwarves gain skills more slowly than in vanilla DF, although like most things, you can turn harder skills on or off. Also, farming is harder. All underground crops can grow at any season, but they take a year to grow. Aboveground crops grow quickly, but are seasonal, so only plant in the spring and summer. You will have access to above ground crop seeds at embark. Use them, they will tide you over until the underground crops come in. It may pay to choose two skilled farmers at embark.
Pets are different, you won't have access to dogs and cats at embark, but a host of more dwarfy, cavern type animals. I like to use leatherwing bats (you can shear them for endless leather, and they hunt vermin) moleweasels (they are super fast, and hunt vermin) and cragtooth boars (shear for ivory, and they are war trainable) and dewbeetles (milk them for beetle dew, brew it into beetle mead.)
Important new buildings: the wood splitting block, built from any block, lets you smooth logs and cut them into 4 planks. The researcher's study lets you research more advanced workshops. The brewery is an improved distillery. Querns and powered millstones now serve different functions, querns mill plants, millstones crush harder things like bone into bonemeal (a flux!) and rock into sand. The screwpress presses oil from leaves, and more. Specialized workshops like the stonecrafters and woodcrafters work with blocks and planks instead of stone and logs, letting you make more with less. The sawmill takes a sawblade to build, and functions as an improved wood splitter. It also lets you cut farmed trees (trees grown in regular farm plots) and get the seeds from them. The crucible lets you make steel and bronze more efficiently, among other things. The scriptorium lets you copy research you have done, to make more than one of any advanced building. But more importantly, it lets you write books. Ten books make a library section, which can raise certain skills up to level four or five.
Magic is a nice addition, you can make a school of wizardry and turn dwarves into arcane dwarves. Research more advanced magic at the school to create elemental wizards of earth, fire, air and water, as well as white and black wizards of three different types.
Priests can pray to Armok to receive goods, useful for getting items for that moody dwarf. Their main use is in ferreting out the secret bad dwarves, though. You might run into dwarven spies, secret necromancers, demon worshippers, or even the Carp Cult!
I'm probably forgetting a lot, so read the manual, it's actually fairly thorough, though maybe a little out of date. If you have further questions, ask on the Masterwork board.