As far as i know, 'hajimemashite' means literally 'let us begin', and is used when meeting someone for the first time.
'yoroshiku onegaishimasu' means something along the lines of 'please be good with me', and is used after 'hajimemashite'. I've seen it also used as a greeting, especially on the internet as 'yoro' or 'yoroshiku', but i don't know if this is actually right