tf.nn.softmax
computes the forward propagation through a softmax layer. You use it during evaluation of the model when you compute the probabilities that the model outputs.
tf.nn.softmax_cross_entropy_with_logits
computes the cost for a softmax layer. It is only used during training.
The logits are the unnormalized log probabilities output the model (the values output before the softmax normalization is applied to them).