I doubt there's any kind of automated program available for cloaking detection (maybe Google has one by now).
One way to see if somebody's cloaking is to look at the search engine results. See what text is displayed describing a website under their link. If that text isn't found anywhere on their page, then they might be cloaking.
Also, if their Google cache doesn't match the website you see displayed they may be cloaking. A lot of cloakers don't allow Google to cache their sites for this reason.
Best technique I've found is surf to the site in question and look at the source. Compare the metas with what the SEs show, they should match. If an SE shows snippets and the snippets are not on the page or not identical, the site MAY be cloaked. Or the site may be updated and the current version is not yet indexed. So check it all again in a few weeks...