I asked a similar question a few days ago and some people said that only the Gold DofE may count as something to fill in for volunteering or skills.
If you are looking for work experience, look for places you can do this that is related to the career that you want to do e.g. if you want to become a vet, volunteer at a local animal rescue centre.
Probably better to do that that DofE if you are only considering DofE for "work experience". But it's apparently fun too.