Substitute goods have positive cross-elasticities of demand: If good A is a substitute for good B, like coffee and tea, then a higher price for B will mean a larger quantity consumed of A.
If the goods are close substitutes, the cross-elasticity will be large, and if they are not close substitutes, the cross-elasticity will be small. Thus, when the cross-elasticity of demand is positive, we are dealing with substitutes, while the size is a measure of how closely substitutable the two goods are.
For instance, Coke and Pepsi, which are close substitutes for most people, will have a large cross-elasticity. However, Coke and orange juice may not be close substitutes for most people, and will therefore have a smaller cross-elasticity.