boys boys boys, it's just acoustics
Obvs there is the physical difference of components (different speakers sound different, duh), but the main contributing factor is
in speakers you get the sound of the music bouncing off all of the surfaces in your room (think reverb, phase issues, standing waves, diffraction, etc)
in headphones --- you don't get that, you just get a direct signal straight to your ears with no reflections.
headphones also allow for accurate use of head related transfer functions (Head-related transfer function - Wikipedia, the free encyclopedia) which allow sound designers/audio engineers to 'mimic' 3d audio (you can use two speakers [read headphones] to trick your brain into thinking a sound is behind you, in front of you, above you, etc), as opposed to just having left and right (1d).
Fun experiment - listen to this in headphones and without headphones, notice a huge difference? It's the transfer functions: YouTube - Virtual Barber Shop (Audio...use headphones, close ur eyes)
Another fun experiment - put some music on through your speakers and walk around your room, turn your head a lot, notice how the sound changes significantly depending on where you are. This is because of the audio reflections bouncing around the room causing phase issues (constructive and destructive interference).
EDIT:
 Originally Posted by Philosopher8659
Through headphones we get the full acoustic effect of an oval shaped chamber.
This is also true - you'll hear the coloration of the headphones resonating... but BARELY, and will most likely be entirely masked by the music (headphones are designed to reduce physical resonance).
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