http://www.visaplace.com/blog-immigration-law/canada-experience-class-applications/faq-canada-experience-class-cec/
Q. If I have already submitted an application for permanent residence as a skilled worker (the traditional way to apply), can I still apply under this category?
Yes, but applicants are required to submit a new application with new fees.
If CIC has not started processing the skilled worker application, the applicant could withdraw it and may be entitled to a refund.
It is not forbidden to apply simultaneously with two different streams of the Economic Class.
However, the applicant will have to choose under which one the permanent resident status will be granted.
Read more: http://www.visaplace.com/blog-immigration-law/canada-experience-class-applications/faq-canada-experience-class-cec/#ixzz2SJx8Vq1O