I'd say that you should just keep using LWP::Simple for your scraping needs until you run into something that it can't do for you, in which case you can start checking the features of the other modules.
The big advantage of LWP::Simple is that it's... well.. simple!
You might also want to check WWW::Mechanize when you start having a need to fill out forms or click buttons on a site, too.
Hanlon's Razor - "Never attribute to malice that which can be adequately explained by stupidity"
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