Definitely liquid over mat, if you want to use both. In my experience, using both really does work better than either one alone, but that's bordering on the compulsive.
It's my understanding that what is added to make sludge thick isn't as effective the fillers used in Spectrum. Multiple coats of Spectrum should be somewhat more effective than a single coat of sludge, but I'd guess by only a small amount. You can apply liquids with a brush to avoid the masking you will have to do if you are going to spray. You'll get a smoother finished surface if you spray.
Some people have used Peel & Seal and other asphalt products without suffering catastrophe, but asphalt will never be as effective as either butyl or a high quality liquid - it has no viscoelasticity. Many people have had terrible problems with asphalt and it isn't just falling off - if it melts, it doesn't matter where it is, it will cause damage. Just as some people can smoke a pack a day for 60 years without dying of a tobaco related desease, some people will get away with putting asphalt in a car. It doesn't mean that it is a smart thing to do. Asphalt is toxic, much less effective and has a significant failure rate.