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Will you be self printing or using a Rapid prototyping service or online printer for the final products.

Also not sure if it's been said but Sketchup is also a very good 3D design app that can be free has mountains of support and has a much lower learning curve than
blender or 3DS and with plugins and open source mods can output just as complicated models. there are also mountains of existing 40k content for it that could make
your modded items easier to produce or at least size and fit.

If nothing else Sketchup is a good way to familiarise yourself with 3D and the way the apps work and 3D planes etc before tackling the big guns.

I use SU and 3DS farely often for junk models as a hobby (make cities and buildings mechs and weapons etc) and have been considering some for use with my Skave if
I could get a reliable prototyper to print them or a 3D printer at a reasonable cost.