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Unlockable Pictures:
Picture 1&2 - Beat DK in floor 1
Picture 3&4 - Beat DK in floor 2
Picture 5&6 - Beat DK in floor 3
Picture 7&8 - Beat DK in floor 4
Picture 9&10 - Beat DK in floor 5
Picture 11&12 - Beat DK in floor 6
Picture 13&14 - Beat DK in floor 7
Picture 15&16 - Beat DK in floor 8
Picture 17 - Beat DK in Roof
Picture 18 - Beat Hidden Boss 1(B1) in basement

Unlockable Movies:
Musical - Beat Hidden Boss 2(B2) in basement.
Ending - Beat the final boss in the Roof.
Introduction - Start a file in Main Game.
Unlock title - screen characters

You can unlock different minis to stroll across the title screen by getting various medals in the game (purely cosmetic). It also changes the music at the title screen to a retro theme:

Toad Minis - Get Bronzes on all 80 levels
Princess Minis - Get Silvers on all 80 levels
Donkey Kong Minis - Get Golds on all 80 levels

Mini Game: Shy Guy Smash:
Collect all of the Cards (One in each level to spell out MINIMARIO) to unlock the Mini Game for that world.

The Minigame is always Shy Guy Smash, but of varying degrees of difficulty and different Pipe layouts.

Beating the Minigames will send you on the way to get the Special Construction Kits:

Special Kit 1 (Mini-Toad) - Beat Three of the Minigames
Special Kit 2 (Mini-Peach) - Beat Six of the Minigames
Special Kit 3 (Mini-DK) - Beat Nine of the Mini-Games

Unlock Hidden Basement Bosses:
After beating the game, you get access to the basement area of the building. From here you can unlock two hidden bosses.

Hidden Boss 1 - Get 40 Silver Stars
Hidden Boss 2 - Get 40 Gold Stars

Unlock construction kits for creating custom levels:
Tropical Island construction kit - Beat Donkey Kong at Tropical Island
Mushroom Mayhem construction kit - Beat Donkey Kong at Mushroom Mayhem
Pipe Works construction kit - Beat Donkey Kong at Pipe Works
Magnet Mania construction kit - Beat Donkey Kong at Magnet Mania
Lava Dome construction kit - Beat Donkey Kong at Lava Dome
Toadstool Castle construction kit - Beat Donkey Kong at Toadstool Castle
Spooky Attic construction kit - Beat Donkey Kong at Spooky Attic
Jungle Hijinks construction kit - Beat Donkey Kong at Jungle Hijinks