I'm not sure if preventive injections are the same as vaccinations. Vaccinations for diptheria, tetanus, polio, mumps, measles, rubella, etc. are taken very seriously in Spain and all doctors and health centers put enormous effort into educating people and making sure all children are vaccinated at the proper times. They're quite successful - I don't have the figures, but the percentage of properly vaccinated children is very high.
If you mean more optional vaccinations for other diseases that only recently have become available, like the one for chicken pox (varicela), I don't know. Maybe someone there now will know. I'd imagine, though, if it isn't used widely, someone would be able to offer it. I have found the Spanish medical community to be very up-to-date.