I keep a small bottle of Morning Fresh (or similar) on my washing machine and any marks "get a dab". My dad always said a bit of detergent was the best stain remover. He always pronounced it DET-er-GENT to make us laugh.
I have some Sard spray on that I just don't use at all. If I need a stain remover I will soak in Vanish powder. Soaking has always been the best method for me. It has bi carb soda in it which is great for removing stains. I don't tend to use stain remover much now that the kids have grown up.
If I am aware I have marked clothing or linen I usually treat the stain immediately with soap, water and elbow grease. My gardening or painting clothes that I wear most days are beyond worrying about and I put them in the wash and let the normal powder deal with what it can.
I would use spray only in the situation that a stain was fresh and I could wash the item right away otherwise it is hand scrub with soap or soak in a Nappy soaker. I have the less toxic type of sprays in the laundry and probably use them every couple of months.
I find the Sard spray the best stain remover. For stubbon stains I soap up and soak overnight but normal stains it's just spray and wash. I've removed that many stubborn stains my daughter has not been able to remove from the teenage childrens' clothes, I think I deserve a medal.