Not anatomically correct, but I think this may be part of the problem.
Face - You establish a very strong sense of direction and perspective with that headpiece. Your face not only doesn't follow it, but the features all sit in different perspectives.
Shoulder - You'll have to tell me what you're going for before I can be certain, but if she's leaning back, her shoulder should move back and not up. When I push out my chest, I feel my shoulder blades rotate inwards toward my spine a little. That pulls my shoulders back. I think you may have to choose either back or up. But not both.
Hope that helps a little. (Also, if you would make a thread about speedpainting or just starting a digital painting in general in the main forum, that would be great. I would love to learn. I don't even know where to start!)
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