The Adobe Photoshop Lightroom 5 Book by Martin Evening has this cryptic sentence (Page 197):

The tone adjustment controls are meant to be applied in the order they appear listed in the Basic Panel.

I thought the order was a matter of indifference, and I understand what Max said that the order doesn't matter (no matter what order you set them, the final result will be the same if the final settings are the same.)

But when I started using the Panel that way, I understood why the adjustments are in the order they are. You have:

1. The white balance/tint controls. These are global, and getting them right lets you see the results of your later controls in the color "context" you set the white balance to. If you change the white balance later, you have to make adjustments to account for crushing the whites and blacks, among other things.
2. The Exposure/contrast control. These are also important to set before playing with the later settings, and changing the Exposure may force you to reconsider them.
3. Highlights/shadows/whites/blacks. Once the previous settings are set to your satisfaction, these let you make adjustments to bring out aspects of the photo that may be under or over-exposed. If the settings above these are altered, you may have to revisit them. Adjusting the Highlights/Shadows after Whites/Blacks can push more pixels into clipping. If you adjust the Highlights/Shadows first, then Whites/Blacks to limit clipping, you get to good results more easily.
4. Presence Panel. These are for tweaking details, nudging saturation and contrast in more subtle ways.

When I understood this, it made working on photos much easier. The order is not set in stone, and there will be times when you have to back up and start re-adjusting, but on the whole the way they are laid out is pretty good.

Actually, the one thing I wish they would move is the lens correction controls. When I correct the photos for vignetting, they brighten enough I will sometimes go back and readjust the exposure slightly. (I wish I could just hard-wire the lens correction to be checked.)