When you save the settings with an empty Cache Location, it does not default to WPSCSS_PLUGIN_DIR . '/cache/'.
I see two problems in class/class-wp-scss.php:
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The isset check on line 167 (and 165 & 166 actually) do not work as expected because WordPress will store an empty string if text fields are empty, which will be evaluated as true, so the value of $cache_dir_setting will be an empty string and not WPSCSS_PLUGIN_DIR . '/cache/'.
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On line 202 it is assumed that the cache dir will be prefixed in the base directory, which is not true for the default setting.