1. Space Dandy
Personally, it's my all time favorite. It's the most eclectic mix of humor, heart, and action. Regarding the plot, the series is like a western show as in there's not an overarching plot. But the way all 26 episodes are weaved and linked together at the end is genius, and the soundtrack is eargasmic.
2. Bartender
If you like drinking your sorrows away, it'd be appropriate to have Bartender on this list too. If you like people telling heartfelt stories about their lives while learning some history 'bout alcohol, then you'll love it.
3. Mobile Suit Gundam War in the Pocket
It wouldn't hurt to have a Gundam series in here somewhere. I think this specific series is one of the best and the most emotional Gundam has to offer and it can be treated as stand alone, so you don't need to watch the original series to have any context. (But go ahead and watch that too! More Gundam doesn't hurt!) All the main characters in there are likable and by the end of its six episodes, I guarantee you'll be attached to them.4. Black Lagoon
If you enjoy gritty, bloody action combined with dark and violent environments alongside a great cast of characters, Black Lagoon is for you. It almost feels like a Grand Theft Auto anime. It's ripe with gang wars and intense violence, so if you like GTA then you'll be right at home.5. Psycho-Pass
It's an anime that makes you think, the best kind of anime! There's a lot of philosophical thoughts involved and it really forces you to think about how society is policed and how society functions as a whole. It's cyberpunk too so lots of flashy technology involved, the opening and endings are eargasmic. In the same cyberpunk vein, you should watch Ghost in the Shell, both the series and the movies. It's known as one of the shows that jumpstarted a cyberpunk craze so you can watch that if you'd like.