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A few days from now I'll be starting off my 40k career by grabbing the Dark Vengeance starter set and upgrading from that. What I want to know are some other sets I should/could buy to make the (750?) point army they start you off with for them able for a competitive scene. Excuse me if I sound like an over-confident noob.

Betrayal of Calth will be good for your money if you are going into the Marines + Transport route.

If you are going bikes then I suggest you getting more bikes ; )

Command squad and Black Knights. (They are alternate builds in the same box) and a Darkshroud.

Black Knights/command squad (they're in the same kit), good competitive units for a DA army.

Another tac squad (since you only get one in DV right?).

And maybe some other vehicles. My suggestion would be a rhino/razorback, or Dark Talon.