This is what I am doing too. I learned a few things... (I have Twilight of the Armor 2.02 that came in the Ultimate Edition)
1) As a starting point, review the Techtree.xml file found in C:\Program Files\Stardock Games\Galactic Civilizations II - Ultimate Edition\Twilight\Data\English. You can open it up in IE to see the code in red text and the data you can modify in black (between the >< characters). There are 362 techs in this file! (A lot of stuff to figure out if you're keen!) How they are listed partially influences the layout seen in the game. Try to learn some of the standards and patterns of syntax the game uses.
2) In C:\Program Files\Stardock Games\Galactic Civilizations II - Ultimate Edition\Twilight\Data\English\TechTrees you'll find the racial tech trees. Here they are simpler in that they refer to the parent info in the main tech tree. Note: the order of the techs in these files doesn't match the main file, but it does not affect the way the game runs.
3) Racial tech trees have differences between each other and the main tech tree. I had to make a spreadsheet to follow it all to figure things out. Reading some other threads here will help orient yourself to some technical details and issues.
4) To make a new tech tree, copy and paste a file like Terran_Techtree.xml and rename it (e.g. mynewrace_Techtree.xml). Then open it up in a text editor, Notepad is ideal, and tinker around, change some costs and some ability bonuses if you like. Be sure to change the InternalName near the top of the file (follow the example that the official game files use), and the display name can be what you like. Install a copy of your new tech tree back into the game directory, start the game, make a custom race and select your new tech tree. And there you go. A simple start 
Once one has played around with this you'll see there are oodles of possibilities...
Creating new techs: try the copy and paste with Notepad in tech tree that you've made. Again follow the example of the official game data as your guide.
Edit: Ninja'ed!!