Hiya,
If you can afford the time to not delve into a CMS first then I would heartily recommend that route yes. Doing this will get you up to scratch with coding proficiently by hand and used to all the bugs that IE throws into the pot as well. Once you have that all sorted and down to a really good standard then you can think about bringing in a CMS.
The great thing about EE is that you can code something that is valid XHTML 1.0 Strict outside of the CMS and when you plug it into the templates it will still be totally valid strict code. EE stays totally out of your way in that respect which is a designers dream 😉
So to re-iterate I would say yes it is great if you can afford the time to learn coding the actual site templates before you try and bring in the CMS part but having said that EE won’t get in your way on that one.
Hope that helps.
Best wishes,
Mark