For free?
Instead of Photoshop, try The GIMP (no really, the 'GNU Image Manipulation Program').
Blueside Union: Starblayde (Blaster), Pax Imperia (Tanker), Pax Britannia (Defender)
Redside Union: Natasha Redshade (Stalker)
There is also a free 3D software called "Blender" if you're interested^^
hmm i have GIMP already (not much good with it) and blnder wasn't working properly 
The gimps a pretty good program to use defnetly recomended it over photoshop/painter if your just going to play about for a bit (why pay hundreads of pounds when you can get basically teh same for free)
others out there are paint.net which is again pretty good and importantly free there's also a program called al.chemy its very basic and really meant for hashing out basic ideas and general random shapes that you can then work up in other programs into something more specific (think of it more as a aid to brake the creative block) but it still has the off interesting feature and some of the things people to with it are pretty neet (take a look on there forums)
another is Artweaver never tried this my self so cant comment on how good/bad it is
and another is Inkscape its free again (woot) i do have this installed but haven't really delved into what i can do. it differs from the Gimp and Art.net tho as it deals with vectors i cant remember the proper definition of vector art but basically you create a shape be it circle, rectangle, whatever you can them enlarge (or shrink) that shape without it becoming pixelated i would guess its a program like this that the city of cute characters are created with as well as Doc destines Art.
ok there's loads of great artwork in this forum and i'm wondering what programes you are using, and if they are free or cheap as i would like to do some stuff like this but can't aford some/most of the software since it's around £100-500