I used to think that the DE was a good way to start because I had gotten the hang of prep and lather but as it turned out I had to learn to lather all over again because lather quality was a big issue for me. Straight razor lather should be more on the wetter side whereas for DE you can get a good shave with almost any kind of lather. So on the whole I think you can safely skip the DEs and start with straights right away as long as you read the material available in the stickies, watch a few vids and get yourself a razor honed by a pro and a cheap strop.
"Nothing would be done at all, if a man waited till he could do it so well, that no one could find fault with it." John Henry Newman