I work for an engineering consultancy which also happens to be a CATIA reseller.
I train lots of guys to use CATIA - both graduates and those who have gone the apprenticeship route and both bring different things to the table. On the whole graduates tend to be more IT literate so pick up the software quicker, but the guys with shopfloor experience have a better grasp of how things should be designed with a view to their manufacture. If you can demonstrate strength in both areas you're on to a winner.
Career wise I would say having enough hours of experience in the software used by your target industry is important. For example if your interested in working in automotive of aerospace having CATIA skills is the way to go. I may be biased but its what most of the industry are using right now particularly if there is an element of surface modelling involved. The customer base is growing into other industries too.
Solid Works has carved out a niche in areas such as product design, fabrication, food processing machinery, oil and gas and medical equipment industies. If you have SW experience these may be the industires to target.
If you're just starting out you may need to be flexible - design engineering vacancies don't always become available on your doorstep and often they will be contract (temporary) roles. If you can demostrate your abilities in a short contract position you may get offered a permanent role (or a longer contract if the contractor lifestyle suits you!).