I guess one of the ways to look at how you could incorporate designer statement pieces into a business casual and classic look would be to have a browse through Vogue or L'Officiel ( another high brow fashion mag) and see how they style things. Or look at the pages that sell designer items - some styling is out there, but some is quite classic.
But I think what is most important is your own personal style and every day needs. The Burberry trench goes with nearly everything (depending on the color of the coat). Try to decide if that is the focal point of the outfit, or you want to add the rockstuds if they are complimenting the coat's color.
One way I have found that does help with styling is to pull out the pieces you are interested in styling, put them together in outfits and take selfies. Then you can evaluate what you got and decide ''oh this blouse doesn't really go that well with the other things, but in outfit 6 it was the star.''
How you wear something depends on your personal likes - perhaps you like an all neutral pallette, maybe you like monochrome.... I'd say experiment with putting together things you have a looking at the results in the selfies. I know it takes a bit of time to try on outfits and decide on the combos - but once you know what works for you it could really make things easier for you. You might find which items in your wardrobe are the ones that you really use and which ones were nice in theory, but a bit impractical in real life. Everyone has a different body shape, height, coloring so I can just give you some general ideas.
Though I think this is in the same eleghunt subculture vein like Banana says. You can use the ideas in the post for free and if that doesn't work for you, you haven't lost any $.
I imagine Banana reading this and then we will see her post this as her new genius, idea. Banana, we are watching you.
