All, except Mothership Zeta.
Broken Steel is number one, as it adds more content to the original story and new enemies to beat. It also raises your level cap by 10.
Others are usual DLCs that have emphasis on a single aspect.
Point Lookout is an adventure DLC.
Operation: Anchorage is a combat DLC.
The Pitt is a story/morality DLC.
Mothership Zeta is... Well... It's something. Has lots of pointless combat, very odd story and barely any exploration.