Almost always the hair and then I try to match the outfit to the hair :)
I usually pick a new favorite item (whether it be the background, or hanging lights, or a new hairstyle) and design my avatar around that!
i usually find one item i like and try to build an outfit around it..
on the current avatar i started out with the "Cuppycake Slip-ons" and it took me agessssss to finish it. well, acually i am still not happy with the shoes..i dont like the slips-ons alone but i cannot find some with a matching color scheme :/
Usually the background, then base the rest around that.

I tend to start with the face & hair; I will then build up an outfit around that while also trying to use newer wearables I have gotten recently.
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I usually start with the hair to be honest. It's easier for me to get the outfit together when I know what the hair will look like.
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A combo of hair and face and then I pick out two or three colors to use as the color scheme.
[img align=center]https://i.imgur.com/HefIbIa.gif[/img]
I find one item I really want to use and then base the rest around it, with maybe a theme in the background.
For this current one I just really wanted to use the sphinx mask, and then everything kind of felt into its own places.
Most of the time I start with a hairstyle and build around it, but sometimes I'll pick out either a new item or eyes/eye makeup to get me started.
Every once in a while I'll open the wardrobe with a theme in mind and just poke around for stuff that matches it.
I usually use the same face sets for a while until I find something else I like but other than that I start with a background to try to build a character from my HA.
[img align=center]https://78.media.tumblr.com/014a37052f368145110da12566f9cc7c/tumblr_om0d2r8Jjf1vkylbjo1_400.gif[/img]
I use my wishlist to keep a running list of interesting wearables that have caught my eye, and when I want to make something new I will go to that list and pick something out.
I usually don't work on the face and hair too much until the end of the process, because it feels way easier to match those to an outfit than the other way around, but I generally start off wearing the and because it's a good neutral face that I find aesthetically pleasing.
With my current HA I started with the jacket cause I thought it was really cute.
Theres usually a specific item I like and I try to use them but it doesnt away work out. For instance, theres this little red bonnet thing with a black ribbon i've been trying to use but have yet to have panned a look for. :P
[img align=center]http://i65.tinypic.com/91m7x2.gif[/img]
I participate in ~HA DAILY ITEM CHALLENGE II~ nearly daily, so I start with that item.
If its a good day, the item will spark some general direction to go in. This happens most often.
If not I look to newly added items to see if any of them will work well with the daily item, and hope that will generate an idea to work with.
The very best days, which don't happen often, I'll have an idea in mind, start working with it and then stumble across an item that completely changes the whole direction.
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Hmm, it totally depends. Sometimes I start on the face, sometimes hair, sometimes chest, sometimes feet, sometimes I'm just going for a general feel that suits my current mood - I usually just scroll through my wardrobe until something strikes my fancy and then I go from there. Or I might be browsing through my wl or someone else's and realize I really like that item, so I get it and build off of there. That's how I wound up with my current HA. It all started from the nose piercing. xD