How I do it (I am not a modder, but perhaps it will help you):
1) I open a custom game with the opponents I want to include on the earth map.
I save the game at 4000 BC and quit. Open the save file in a text editor.
2) I then open the Earth map scenario on a text editor.
You have two things to change: at the beginning you have the teams definition, and then the leader/civilization for each team. Change the civs and leaders you want to drop with the info you find in the 4000 BC save. (In the team definition you have to change the starting techs, in the other part, the name of leader, his traits, colors, etc...) A Copy/Paste excercise...
Save again the scenario under your favorite name.
3) Open the modified scenario with civIV, selecting the first civ in the list (otherwise, when editing the save with worldbuilder, you will notice that the civs which are before you in the list have already settled their cap).
On first turn, before doing anything, open the world builder. Modify the place of the starting units of the modified civs (select the player layer, select a leader, then go select a unit on the window in the left of the screen. Left click on the map to add the selected unit, right click to remove). Save. Exit WorldBuilder.
4) Enjoy.
It's possible I missed steps, but I can't acces the XML files right now, so it's from memory. I suggest you post on the customisation forum to have more detailed tips
Cheers,
Raskolnikov