1. You create them via xml. The color pallete that comes with the game is very limited, has only a selection of colors for each faction plus a bunch for relics/asteroids and the like. Aiden made a new color pallete that hase 256 colors to choose from, I use this for my 50 new ship colors added with GST. This is an example of one of them colors:
<GC3Appearance>
<InternalName>ST_Krenim_R_Appearance</InternalName>
<DisplayName>Ship_Color_ST_Krenim_R</DisplayName>
<!-- Needs to be created with paint.net or the likes if you do not the game will use a plain white swatch and looks ugly-->
<DisplayIcon>Krenim_R_Appearance_Icon.png</DisplayIcon>
<!-- Ship Colours. Taken from GradientMap.png (Numbers 0-255, 0 been the top, 255 the bottom)-->
<DiffuseGradientRow1>60</DiffuseGradientRow1>
<DiffuseGradientRow2>0</DiffuseGradientRow2>
<!-- Main Lights Taken from GradientMapLights.png (Numbers 0-255, 0 been the top, 255 the bottom)-->
<LightGradientRow1>65</LightGradientRow1>
<!-- Cockpit & Secondary lights Taken from GradientMapLights.png (Numbers 0-255, 0 been the top, 255 the bottom)-->
<LightGradientRow2>69</LightGradientRow2>
<!--Engine Taken from GradientMapLights.png (Numbers 0-255, 0 been the top, 255 the bottom)-->
<LightGradientRow3>65</LightGradientRow3>
<!-- Materials (These control how much of the materials set in FactionDefs.xml get displayed on the hull of ships) -->
<SurfaceScale1>10.0</SurfaceScale1>
<SurfaceWeight1>1.0</SurfaceWeight1>
<SurfaceScale2>20.0</SurfaceScale2>
<SurfaceWeight2>1.0</SurfaceWeight2>
<!-- Engine Colour in RGB -->
<EngineColor>
<Red>50</Red>
<Green>50</Green>
<Blue>250</Blue>
<Alpha>255</Alpha>
</EngineColor>
</GC3Appearance>
You can choose to overwrite the default pallete with a new one, or simply add a new pallete and point the game to it from GraphicAssets.xml and Crusade_GraphicAssets.xml. Either way addign a new pallete without the default colors in it (there is a combined pallete on the Nexus of default + aidens) will result in you changing all the default colors. Takes a bit of time to go through and set them right.
2. Do not think the UI is built for this. It requires set themes that are in the xml tables, like the example above. To do them on the fly within the game it would have to create xmls and art, just do not think the game is built for that atm.