How would I create something like the images attached? I currently use illustrator, but I would like to develop my skills, to create something like the attached - I do not know if photoshop is how I would go about creating something like this?
The first one is an illustration, so if youre an artist you would paint it. The second one is, as Derek said, a composite. It looks to me like a comp of a photo and a painting. I second the advice to look at tutorials. Here's a good one by Colin Smith (and you can find many more by googling):
What are you creating this for exactly -- the web, video, print, product packaging, something else? I ask because final output is everything. It determines which tools and specifications you should use to create your artwork.
Illustrator is best for math-based vector output such as logos, drawings, icons, cartoons, illustrations and other flat colored images. Photoshop is mainly for pixel-based raster images (photography & bitmaps).
To learn to composite in Photoshop, look on YouTube for Jesus Ramirez -- the Photoshop Training Channel.