Yes, you can. Because it is easy to see by inspection that those 4 elements are linearly dependent. It is also good to spot easy things. And it will work in general, since that new set of vectors is a basis if and only if you can expess u,v,w as combinations of the three new ones, and it is easy to see how to do that by eye. In general, you need to set up and solve some simultaneous equations. In this case you can see the solution without doing and linear algebra.
As for your other question: you know how to solve simultaneous equations, so do it. Find the a,b,c such that a(u+v)+b(v-w)+c(w-u)=0, and show that the only solution is for a=b=c=0. Note you have to rearrange to write things in terms of u,v,w which are known to be a basis. More succintly, note this implies (a-c)u+(a+b)v+(c-b)w=0, so since, u,v,w are a basis, this implies a-c=a+b=c-b=0, whence a=b=c=0.