Your wife (I assume?) is indeed lovely!
A couple of things to look at: The lighting on her eyes, and the shadow patterns on her face. In the first image, look at the shadow cast over her eye by her nose, compared to the brightness of the other eye. When seeing the full face, we like to see the eyes lit up more evenly, or at least without a sharp shadow cast across. Moving the light up a tad and a little bit more toward the centerline of her face (or moving her face correspondingly) would bring the shadow off of her eye, and would cast a "Rembrandt shadow." It would also eliminate the shadow from the side of her mouth which is cast from her natural facial features.
Now that I've said that, your second image flips over to the opposite, that is a heavy side-light with the shadowline running down the center of her face. This often produces a desirable dramatic effect (look at my avatar, which is me, shot by DDC Studios - he'll chime in in a bit I'm sure). Notice that both of my eyes are lit, but half of my face is dark. To improve this image, I would only say that your light is a bit hot, causing some overexposure on the side of her face toward the light (blown highlights). This again is not a bad thing and is often desirable when used with control.
Is your light adjustable? If it is, I would back it down a bit with the same camera settings. If it isn't, I would close down the aperture a bit to reduce the direct-light exposure, and then I'd fiddle with the shutter speed to affect the background (ambient) light exposure. For a better explanation of what I'm talking about (and what it does), do a search in the forum for "dragging the shutter" or maybe Rolando still has a link to his tutorial on the front page of the site. Let's keep it simple before tackling the minutae of Photoshop stuff. Well done for the first time out!