My own choices, as a pretty big action figure collector:
Movie-accurate Ghostbusters: Peter Venkman, Ray Stantz, Egon Spengler, and Winston Zeddmore, all the the likenesses of Bill Murray, Dan Aykroyd, Harold Ramis, and Ernie Hudson.
Fight Club: Tyler Durden and the unnamed narrator (Brad Pitt and Edward Norton).
Pulp Fiction: Vincent Vega and Jules Winfield (John Travolta and Samuel L. Jackson).
Chow Yun-Fat in a suit with twin 45s, as he appeared in The Killer or Hard Boiled.
Comic book characters from DC Direct: Booster Gold to round out the JLI, Jack Marlowe, Grifter, Savant, Tao, Holden Carver, and Miss Misery (mostly from Wildcats 3.0 and Sleeper).
Other comic book characters: Reuben Flagg from American Flagg! (with Raul the cat), The Rocketeer, and more Mike Allred-designed characters.
A GOOD Elvis figure.
A GOOD Bettie Page.
A GOOD Neo from The Matrix.
(None of those have been done “right” by any sculptors or toy companies yet.)
Musicians: Tom Waits, Brian Setzer, Ben Folds, Tori Amos, Gwen Stefani, Nick Cave, Morrissey, Neko Case, Reverend Horton Heat, Mike Ness, and an entire “Legends of Jazz” series, all with good likenesses, decent articulation, no pre-posed stances, and realistic-looking instruments!