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There are technical considerations such as old browser support for pure CSS designs, which can make it fiddlier than using tables to get that perfect design.
It depends on how much and what sort of content needs to be displayed. If you have a lot of lists to display then tables can be easier for the page lay out. If you have minimal text and a few images then a pure CSS could be the way forward.
Make sure you check HTML and CSS with w3.org's validators and you will be on the right track.
In fact, you can learn so much that I'm forever grateful I waded in. It was probably the best single professional step I've ever taken. I understand HTML better, I understand browsers better, and I understand the difference between print and the web MUCH better.
This has influenced my design choices, my consultations with clients, and my ability to get better ranking on search engines -- even when I use tables. The pages I create communicate more clearly to the end user, and their usability often gets high praise.
Although I won't win any design awards, I'm not looking for that. An award will not buy me dinner, but traffic that converts and brings in a good ROI, that will buy my groceries and then some.
Finally I got brave enough to dive in full on & have been using it for about 6 months.
My first designs were still table / css hybrids, but even that is being abandoned for full on CSS layout.
Go for it.